博士（工学）, 京都大学

mechanochemical synthesis

Cu(I)-catalyzed Borylation

mechanochromism

発光性金属錯体

有機金属化合物

有機金属

organometallics

Manufacturing Technology (Mechanical Engineering, Electrical and Electronic Engineering, Chemical Engineering), Electron device and electronic equipment

Life Science, Bioorganic chemistry

Nanotechnology/Materials, Structural organic chemistry and physical organic chemistry

Nanotechnology/Materials, Synthetic organic chemistry

Bachelor's degree program, School of Engineering

Master's degree program, Graduate School of Chemical Sciences and Engineering

Doctoral (PhD) degree program, Graduate School of Chemical Sciences and Engineering

2015, 永瀬財団, 長瀬研究振興賞
伊藤 肇

2014, 日本化学会学術賞
伊藤 肇

2011, 北海道大学研究総長賞
伊藤 肇

2008, 有機合成化学奨励賞
Japan

Using Mechanochemistry to Activate Poly(vinyl chloride) as a Mechanotunable Brønsted-Acid-Releasing Reagent for Organic Synthesis
Koji Kubota; Reon Hisazumi; Kalipada Jana; Julong Jiang; Tsubura Endo; Satoshi Maeda; Hajime Ito
Journal of the American Chemical Society, American Chemical Society (ACS), 02 Jan. 2026
Scientific journal

Mechanochemical synthesis of organosodium compounds through direct sodiation of organic halides
Keisuke Kondo; Matthew Lowe; Nathan Davison; Paul G. Waddell; Roly J. Armstrong; Erli Lu; Koji Kubota; Hajime Ito
Nature Synthesis, Springer Science and Business Media LLC, 08 Dec. 2025
Scientific journal

All-step mechanochemical approach for the rapid and solventless synthesis of Boscalid
Asahi Nagao; Koji Kubota; Hajime Ito
Synthesis, Georg Thieme Verlag KG, 11 Nov. 2025
Scientific journal, Boscalid, the active ingredient in various fungicides used in large quantities worldwide, is traditionally synthesized using solutionbased methods that require substantial quantities of reaction solvents and prolonged reaction times, highlighting opportunities for improvement in waste reduction, time efficiency, and energy consumption. Herein, we report a solventless and rapid synthesis of Boscalid via an all-step mechanochemical reaction. This synthetic route comprises three steps: Suzuki-Miyaura cross-coupling, zinc-mediated Béchamp reduction, and amidation with 2-chloronicotinyl chloride. Each mechanochemical reaction proceeded rapidly, and the total reaction time was significantly shorter than that of previous methods. Notably, all synthetic operations can be carried out without an inert gas atmosphere or a large amount of solvent, both of which are required under conventional solution-based conditions. Furthermore, gramscale synthesis was successfully achieved without any yield loss at each step, highlighting the potential scalability of this protocol.

Computational Exploration of Polymer Mechanochemistry: Quantitation of Activation Force and Systematic Discovery of Reaction Sites by the Extended Artificial Force-Induced Reaction Method
Julong Jiang; Koji Kubota; Yu Harabuchi; Mingoo Jin; Zhi Jian Wang; Tasuku Nakajima; Hajime Ito; Jian Ping Gong; Satoshi Maeda
Journal of the American Chemical Society, American Chemical Society (ACS), 29 Aug. 2025
Scientific journal

Introducing Steric Bulk into Silylboranes: Enhanced Bench Stability and Novel Chemical Reactivity
Rikuro Takahashi; Julong Jiang; Satoshi Maeda; Hajime Ito
Angewandte Chemie International Edition, Wiley, 23 Jun. 2025
Scientific journal, Silylboranes are versatile intermediates in organic synthesis, and a wide range of structural variants of silylboranes have already been synthesized. However, the stability of silylboranes varies significantly, and their decomposition mechanism remains to be fully understood. Moreover, some silylborane motifs have not yet been applied as synthetic reagents due to their instability. To address this issue, we first investigated the decomposition mechanism of silylboranes in air and moisture using experimental and theoretical methods. We discovered that oxygenation by atmospheric oxygen is the major decomposition pathway, resulting in the formation of a borylsilylether, and that the introduction of a bulky silyl group suppresses this decomposition. Based on these results, we synthesized triisopropylsilyldimesitylborane (i‐Pr3Si–BMes2), which exhibits high bench stability. Moreover, i‐Pr3Si–BMes2 reacts with carbon monoxide (CO), which is the first example for a reaction between a silylborane and CO. Further computational studies revealed that electronic effects, including hyperconjugation between the Si–B σ‐bond and C–O π*‐bond, are crucial for CO activation. Furthermore, we prepared a bench‐stable bissilylaminoborane by introducing triisopropylsilyl groups, providing a bissilylchloroborane upon hydrogen chloride treatment. These findings provide valuable insights into how steric and electronic effects can be used to optimize the balance between stability and reactivity in silylboranes.

Mechanochemical activation of metallic lithium for the generation and application of organolithium compounds in air
Keisuke Kondo; Koji Kubota; Hajime Ito
Nature Synthesis, Springer Science and Business Media LLC, 21 Feb. 2025, [Peer-reviewed], [Corresponding author]
Scientific journal

A Cooperative Electron-Deficient Phosphine/Olefin Ligand System for the Site-Selective Mechanochemical Suzuki–Miyaura Cross-Coupling of 2,4-Dibromoaryl Ethers
Yunpeng Gao; Julong Jiang; Satoshi Maeda; Koji Kubota; Hajime Ito
Chemical Science, Royal Society of Chemistry (RSC), 2025
Scientific journal, The palladium-catalyzed site-selective cross-coupling of identical halogen groups with minimal electronic and steric bias remains a formidable challenge, especially for simple benzene derivatives. Here, we report a cooperative phosphine/olefin ligand...

Solid-State Aromatic Nucleophilic Fluorination: A Rapid, Practical, and Environmentally Friendly Route to N-Heteroaryl Fluorides
Koji Kubota; Tetsu Makino; Keisuke Kondo; Tamae Seo; Mingoo Jin; Hajime Ito
Green Chemistry, Jan. 2025, [Peer-reviewed], [Corresponding author]

Solvent-free Zinc-mediated Béchamp Reduction Using Mechanochemistry
Koji Kubota; Asahi Nagao; Hajime Ito
RSC Mechanochemistry, Royal Society of Chemistry (RSC), 2025, [Peer-reviewed], [Corresponding author]
Scientific journal, In this study, we report the first mechanochemical protocol for highly efficient solvent-free Béchamp reduction using inexpensive Zn metal as a reductant in combination with NH4Cl. This reaction is considerably...

Scaling theory for the kinetics of mechanochemical reactions with convective flow
Tetsuya Yamamoto; Koji Kubota; Yu Harabuchi; Hajime Ito
RSC Mechanochemistry, Royal Society of Chemistry (RSC), 2025, [Peer-reviewed], [Corresponding author]
Scientific journal, Mechanochemical organic synthesis using ball milling is a powerful and versatile technique that leverages mechanical energy to drive chemical reactions, offering a more energy-efficient and environmentally-friendly alternative to conventional solution-based...

Solid-state Dynamics of Binuclear N-Heterocyclic Carbene Au(I) Rotor with para-Phenylene Rotator
Pingyu Jiang; Alexander S Mikherdov; Hajime Ito; Mingoo Jin
Chemistry Letters, Oxford University Press (OUP), 11 Jul. 2024, [Peer-reviewed], [Corresponding author]
Scientific journal, Abstract

Molecular dynamics in the crystalline solid state, typically constrained by a densely packed crystal environment, may offer opportunities to control the physical properties of solid-state materials. In this work, a neutral crystalline molecular rotor featuring a para-phenylene rotator encapsulated by N-heterocyclic carbene ligands and connected via a C-Au-C rotational axis is presented. Single-crystal X-ray diffraction studies, along with variable-temperature solid-state 2H NMR spin-echo measurements, confirm the presence of 180° 2-fold rotational dynamics of the para-phenylene moiety in the solid state.

Crystallization-Induced Chirality Transfer in Conformationally Flexible Azahelicene Au(I) Complexes with Circularly Polarized Luminescence Activation
Pingyu Jiang; Alexander S. Mikherdov; Hajime Ito; Mingoo Jin
Journal of the American Chemical Society, 146, 18, 12463, 12472, American Chemical Society (ACS), 16 Apr. 2024, [Peer-reviewed], [Corresponding author]
Scientific journal

Dissolution-Limited Reactions in Solid-State Synthesis
Tetsuya Yamamoto; Koji Kubota; Hajime Ito
Nihon Reoroji Gakkaishi, 52, 2, 161, 170, Society of Rheology Japan, 15 Apr. 2024, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Solid-state nickel(0)-mediated Yamamoto coupling enabled by mechanochemistry
Koji Kubota; Naoki Shizukuishi; Shotaro Kubo; Hajime Ito
Chemistry Letters, Oxford University Press (OUP), 04 Apr. 2024, [Peer-reviewed], [Corresponding author]
English, Scientific journal, Abstract

Herein, we report the first solid-state protocol for nickel(0)-mediated Yamamoto coupling reactions using ball milling. A variety of aryl halides reacted efficiently in the presence of bis(cyclooctadiene)nickel(0) [Ni(cod)2] and 4,4'-di-tert-butyl-2,2'-bipyridyl under solid-state mechanochemical conditions, affording the corresponding biaryls in high yields. Considering that potentially harmful and high-boiling organic solvents are not required, the present study provides a more convenient, environmentally friendly, and sustainable alternative to conventional solution-based Yamamoto coupling. Solid-state Yamamoto coupling polymerization and the development of a catalytic variant are also described.

Highly Efficient and Air-tolerant Calcium-based Birch Reduction Using Mechanochemistry
Koji Kubota; Yamato Fukuzawa; Keisuke Kondo; Yunpeng Gao; Hajime Ito
Chemistry Letters, Oxford University Press (OUP), 04 Apr. 2024, [Peer-reviewed], [Corresponding author]
English, Scientific journal, Abstract

In this study, we report a mechanochemical protocol for highly efficient and air-tolerant calcium-based Birch reduction. The developed mechanochemical approach allows the use of readily available calcium metal as a safer-to-handle reductant for Birch reduction of various aromatic compounds. The reaction was rapid, and the desired dearomatization products were obtained in good yields within 15 min at ambient temperature. Notably, all synthetic operations can be performed under ambient conditions without a complicated reaction setup involving inert gases. The feasibility of the gram-scale synthesis was demonstrated, further highlighting the practical utility of this protocol.

Mechanochemistry enabling highly efficient Birch reduction using sodium lumps and D-(+)-glucose
Keisuke Kondo; Koji Kubota; Hajime Ito
Chemical Science, Feb. 2024, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Ring Expansion of Cyclic Boronates via Oxyboration of Arynes
Yuma Shiratori; Julong Jiang; Koji Kubota; Satoshi Maeda; Hajime Ito
Journal of the American Chemical Society, American Chemical Society (ACS), 10 Jan. 2024, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Mechanochemical Generation of Aryl Barium Nucleophiles from Unactivated Barium Metal
Koji Kubota; Sota Kawamura; Julong Jiang; Satoshi Maeda; Hajime Ito
Chemical Science, Royal Society of Chemistry (RSC), 2024, [Peer-reviewed], [Corresponding author]
Scientific journal, Organobarium reagents are of interest as homologues of the Grignard reagents based on organomagnesium compounds due to their unique reactivity as well as regio- and stereoselectivity. However, reactions involving organobarium...

Direct arylation of alkyl fluorides using in situ mechanochemically generated calcium-based heavy Grignard reagents
Pan Gao; Julong Jiang; Yamato Fukuzawa; Satoshi Maeda; Koji Kubota; Hajime Ito
RSC Mechanochemistry, Royal Society of Chemistry (RSC), 2024, [Peer-reviewed], [Corresponding author]
Scientific journal, Here, we report the reaction of calcium-based heavy Grignard reagents, which are easily generated by a mechanochemical method, with unactivated alkyl fluorides in the absence of transition metal catalysts to...

Mechanochemistry Enabled Highly Efficient Solvent-Free Deoxygenation of Phosphine Oxides in Air
Koji Kubota; Reon Hisazumi; Tamae Seo; Hajime Ito
RSC Mechanochemistry, Royal Society of Chemistry (RSC), 2024, [Peer-reviewed], [Corresponding author]
Scientific journal, Deoxygenation of phosphine oxides is an important method for the synthesis of valuable organophosphine compounds and recycling of phosphorus resources. However, existing solution-based deoxygenation protocols usually require long reaction times,...

Solid-State Mechanochemistry for the Rapid and Efficient Synthesis of Tris-Cyclometalated Iridium(III) Complexes
Koji Kubota; Tsubura Endo; Hajime Ito
Chemical Science, Royal Society of Chemistry (RSC), 2024, [Peer-reviewed], [Corresponding author]
Scientific journal, Tris-cyclometalated iridium(III) complexes have received widespread attention as attractive prospective materials for e.g., organic light-emitting diodes (OLEDs), photoredox catalysts, and bioimaging probes. However, their preparation usually requires prolonged reaction times,...

Using Mechanochemistry to Activate Commodity Plastics as Initiators for Radical Chain Reactions of Small Organic Molecules
Koji Kubota; Julong Jiang; Yuri Kamakura; Reon Hisazumi; Tsubura Endo; Daiyo Miura; Shotaro Kubo; Satoshi Maeda; Hajime Ito
Journal of the American Chemical Society, American Chemical Society (ACS), 22 Dec. 2023, [Peer-reviewed], [Corresponding author]
Scientific journal

Mechanochemical Synthesis of Non‐Solvated Dialkylalumanyl Anion and XPS Characterization of Al(I) and Al(II) Species**
Satoshi Kurumada; Ryotaro Yamanashi; Kengo Sugita; Koji Kubota; Hajime Ito; Satoru Ikemoto; Chaoqi Chen; Takumi Moriyama; Satoshi Muratsugu; Mizuki Tada; Takanori Koitaya; Taisuke Ozaki; Makoto Yamashita
Chemistry – A European Journal, Wiley, 11 Dec. 2023, [Peer-reviewed], [Corresponding author]
Scientific journal, Abstract

A non‐solvated alkyl‐substituted Al(I) anion dimer was synthesized by a reduction of haloalumane precursor using a mechanochemical method. The crystallographic and theoretical analysis revealed its structure and electronic properties. Experimental XPS analysis of the Al(I) anions with reference compounds revealed the lower Al 2p binding energy corresponds to the lower oxidation state of Al species. It should be emphasized that the experimentally obtained XPS binding energies were reproduced by delta SCF calculations and were linearly correlated with NPA charges and 2p orbital energies.

A Steric-Repulsion-Driven Clutch Stack of Triaryltriazines: Correlated Molecular Rotations and a Thermoresponsive Gearshift in the Crystalline Solid
Mingoo Jin; Ryunosuke Kitsu; Natsumi Hammyo; Ayana Sato-Tomita; Motohiro Mizuno; Alexander S. Mikherdov; Mikhail Tsitsvero; Andrey Lyalin; Tetsuya Taketsugu; Hajime Ito
Journal of the American Chemical Society, American Chemical Society (ACS), 07 Dec. 2023, [Peer-reviewed], [Corresponding author]
Scientific journal

Single Crystal Growth of Cyclopenta-Fused Polycyclic Aromatic Hydrocarbon by the Naphthalene Flux Method: 2D Ambipolar Charge Transport Properties and NIR Absorption
Hirohiko Tanoguchi; Takuma Yuki; Seiya Yokokura; Takashi Yanase; Mingoo Jin; Hajime Ito; Taro Nagahama; Toshihiro Shimada
ACS Applied Electronic Materials, 26 Oct. 2023, [Peer-reviewed], [Corresponding author]
Scientific journal

Stereospecific synthesis of silicon-stereogenic optically active silylboranes and general synthesis of chiral silyl anions
Xihong Wang; Chi Feng; Julong Jiang; Satoshi Maeda; Koji Kubota; Hajime Ito
Nature Communications, Sep. 2023, [Peer-reviewed], [Corresponding author]

Giant Crystalline Molecular Rotors that Operate in the Solid State.
Rempei Ando; Ayana Sato-Tomita; Hajime Ito; Mingoo Jin
Angewandte Chemie (International ed. in English), e202309694, 31 Aug. 2023, [Peer-reviewed], [Corresponding author], [International Magazine]
English, Scientific journal, Molecular motion in the solid state is typically precluded by the highly dense environment, and only molecules with a limited range of sizes show such dynamics. Here, we demonstrate the solid-state rotational motion of two giant molecules, i.e., triptycene and pentiptycene, by encapsulating a bulky N-heterocyclic carbene (NHC) Au(I) complex in the crystalline media. To date, triptycene is the largest molecule (surface area: 245 Å2 ; volume: 219 Å3 ) for which rotation has been reported in the solid state, with the largest rotational diameter among reported solid-state molecular rotors (9.5 Å). However, the pentiptycene rotator that is the subject of this study (surface area: 392 Å2 ; volume: 361 Å3 ; rotational diameter: 13.0 Å) surpasses this record. Single-crystal X-ray diffraction analyses of both the developed rotors revealed that these possess sufficient free volume around the rotator. The molecular motion in the solid state was confirmed using variable-temperature solid-state 2 H spin-echo NMR studies. The triptycene rotor exhibited three-fold rotation, while temperature-dependent changes of the rotational angle were observed for the pentiptycene rotor.

Dual Nickel(II)/Mechanoredox Catalysis: Mechanical-force-driven Aryl-amination Reactions Using Ball Milling and Piezoelectric Materials
Tamae Seo; Koji Kubota; Hajime Ito
Angewandte Chemie International Edition, 29 Aug. 2023, [Peer-reviewed], [Corresponding author]

Iterative Synthesis of Oligosilanes Using Methoxyphenyl- or Hydrogen-Substituted Silylboronates as Building Blocks: A General Synthetic Method for Complex Oligosilanes
Takumi Takeuchi; Avijit Roy; Hajime Ito
Journal of the American Chemical Society, 145, 29, 16249, 16260, American Chemical Society (ACS), 12 Jul. 2023, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Construction of a Helical Structure with a Parallel Alignment of Molecular Dipoles in Crystals by Utilizing a Halogen-3 Synthon and a Bulky Silyl Spacer
Natsumi Hammyo; Mingoo Jin; Hajime Ito
Crystal Growth & Design, American Chemical Society (ACS), 08 May 2023, [Peer-reviewed], [Corresponding author]
Scientific journal

An Improved Catalytic System for Solid-state Iridium(I)-catalyzed C–H Borylation Using Mechanochemistry
Keisuke Kondo; Tatsuo Ishiyama; Koji Kubota; Hajime Ito
Chemistry Letters, The Chemical Society of Japan, 05 Apr. 2023, [Peer-reviewed], [Corresponding author]
Scientific journal

Luminescent Mechanochromism and the Photosalient Effect of Aryl Gold(I) Isocyanide Complexes
Tomohiro Seki; Hajime Ito
The Materials Research Society Series, 53, 85, Springer Nature Singapore, 28 Mar. 2023, [Peer-reviewed], [Corresponding author]
In book, Abstract

A study of stimuli-responsive molecules that can change their physical properties or external shape owing to variations in the external environment has attracted much attention owing to potential application in sensors and actuators. Our group has intensively studied aryl gold(I) isocyanide complexes to develop stimuli-responsive molecular crystals that can show luminescent mechanochromism and crystal jumping through phase transitions induced by mechanical stimulation or photoirradiation. Interestingly, some of our gold(I) isocyanide complexes have crystalline or even single crystalline characteristic both before and after mechano-induced emission color changes or photoinduced crystal jump. Based on the detailed information on molecular arrangements of the aryl gold(I) isocyanide complexes, the underlying mechanism of the responses can be clearly identified. In the Sect. 5.2 of this chapter, we review luminescent mechanochromic aryl gold(I) isocyanide complexes that has unique characteristic such as multiple emission colors, infrared emission, and noncentrosymmetry/centrosymmetry switching. Section 5.3 describes the mechano-induced single-crystal-to-single-crystal phase transitions of aryl gold(I) isocyanide complexes with red- and blue-shifted emission color changes or reversibility. In Sect. 5.4, the photoinduced phase transition of a gold(I) complex which accompanied by mechanical motion, i.e., crystal jump is described.

In Situ and Real-Time Visualization of Mechanochemical Damage in Double-Network Hydrogels by Prefluorescent Probe via Oxygen-Relayed Radical Trapping.
Yong Zheng; Julong Jiang; Mingoo Jin; Daiyo Miura; Fei Xue Lu; Koji Kubota; Tasuku Nakajima; Satoshi Maeda; Hajime Ito; Jian Ping Gong
Journal of the American Chemical Society, 145, 13, 7376, 7389, 23 Mar. 2023, [Peer-reviewed], [Corresponding author], [International Magazine]
English, Scientific journal, Visualization of mechanochemical damages, especially for those in the molecular-scale (e.g., bond scission in polymeric materials), is of great industrial and academic significance. Herein, we report a novel strategy for in situ and real-time visualization of mechanochemical damages in hydrogels by utilizing prefluorescent probes via oxygen-relayed free-radical trapping. Double-network (DN) hydrogels that generate numerous mechanoradicals by homolytic bond scission of the brittle first network at large deformation are used as model materials. Theoretical calculation suggests that mechanoradicals generated by the damage of the first network undergo an oxygen-relayed radical-transfer process which can be detected by the prefluorescent probe through the radical-radical coupling reaction. Such an oxygen-relayed radical-trapping process of the prefluorescent probe exhibits a dramatically enhanced emission, which enables the real-time sensing and visualization of mechanochemical damages in DN hydrogels made from brittle networks of varied chemical structures. To the best of authors' knowledge, this work is the first report utilizing oxygen as a radical-relaying molecule for visualizing mechanoradical damages in polymer materials. Moreover, this new method based on the probe post-loading is simple and does not introduce any chemical structural changes in the materials, outperforming most previous methods that require chemical incorporation of mechanophores into polymer networks.

Mechanochemical Approach for Air‐Tolerant and Extremely Fast Lithium‐Based Birch Reductions in Minutes
Yunpeng Gao; Koji Kubota; Hajime Ito
Angewandte Chemie International Edition, 62, 21, e202217723, Wiley, 21 Mar. 2023, [Peer-reviewed], [Corresponding author]
Scientific journal

Mechanochemistry-Directed Ligand Design: Development of a High-Performance Phosphine Ligand for Palladium-Catalyzed Mechanochemical Organoboron Cross-Coupling
Tamae Seo; Koji Kubota; Hajime Ito
Journal of the American Chemical Society, 145, 12, 6823, 6837, American Chemical Society (ACS), 09 Mar. 2023, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Multidynamic Crystalline Molecular Rotors Comprising an N-Heterocyclic Carbene Binuclear Au(I) Complex Bearing Multiple Rotators
Mingoo Jin; Satsuki Matsuura; Hikaru Yamamoto; Motohiro Mizuno; Hajime Ito
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 26, 12, e202201468, Feb. 2023, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Solid-State Silver-Catalyzed Ring-Opening Fluorination of Cyclobutanols by Using Mechanochemistry
Ryota Isshiki; Koji Kubota; Hajime Ito
Synlett, Georg Thieme Verlag KG, 29 Jan. 2023, [Peer-reviewed], [Corresponding author]
Scientific journal, Abstract

In this report, we demonstrate that a ball-milling technique facilitates fast and efficient silver-catalyzed ring-opening fluorination of cyclobutanols. This is the first report of a catalytic C–C bond-cleavage/functionalization reaction under solid-state mechanochemical conditions. The developed protocol affords a high yield of γ-fluorinated ketones within much shorter reaction times, and requires less silver catalyst and Selectfluor compared with the previous solution-based conditions. Notably, the process can be carried out in air. Because of the reduced use of chemicals and the simple time-saving experimental procedures, this technique is an efficient and environmentally friendly way to access γ-fluorinated ketones.

Solid-state mechanochemical cross-coupling of insoluble substrates into insoluble products by removable solubilizing silyl groups: uniform synthesis of nonsubstituted linear oligothiophenes
Koji Kubota; Keisuke Kondo; Tamae Seo; Mingoo Jin; Hajime Ito
RSC Advances, 13, 41, 28652, 28657, Royal Society of Chemistry (RSC), 2023, [Peer-reviewed], [Corresponding author]
Scientific journal, We developed a new solid-state mechanochemical strategy using a removable and solubilizing silyl group that enables the organic transformation of insoluble substrates into insoluble products.

Exploring Au(i) involving halogen bonding with N-heterocyclic carbene Au(i) aryl complexes in crystalline media
Alexander S. Mikherdov; Mingoo Jin; Hajime Ito
Chemical Science, 14, 17, 4485, 4494, Royal Society of Chemistry (RSC), 2023, [Peer-reviewed], [Corresponding author]
Scientific journal, The halogen bonding involving the Au(i) metal center was systematically studied using a series of nine co-crystals between NHC Au(i) aryl complexes and iodoperfluoroarenes through XRD and solid-state NMR techniques, as well as DFT calculations.

Mechanochemical protocol facilitates the generation of arylmanganese nucleophiles from unactivated manganese metal
Rina Takahashi; Pan Gao; Koji Kubota; Hajime Ito
Chemical Science, 14, 3, 499, 505, Royal Society of Chemistry (RSC), 2023, [Peer-reviewed], [Corresponding author]
Scientific journal, A ball-milling approach allows the efficient activation of unactivated manganese metal and thus makes the direct generation of arylmanganese nucleophiles feasible without the need for complicated pre-activation processes and metal additives.

Computational Exploration of Polymer Mechanochemistry: Quantitation of Activation Force and Systematic Discovery of Reaction Sites Utilizing Two Forces
Julong Jiang; Koji Kubota; Mingoo Jin; Zhi Jian Wang; Tasuku Nakajima; Hajime Ito; Jian Ping Gong; Satoshi Maeda
American Chemical Society (ACS), 23 Nov. 2022, [Peer-reviewed], [Corresponding author]
A series of mechanophores were studied computationally by employing the AFIR (Artificial Force Induced Reaction) method, which applies an artificial force on the molecule to trigger reactions, and meanwhile with a tensile force to simulate a mechanochemical reaction. The calculation results were both qualitatively and quantitatively consistent to those reported experimentally, indicating that the AFIR is a reliable approach to studying mechanochemical reactions. It was then applied to the study of retro-Diels-Alder reactions for the theoretical predictions of activation force levels which are currently unavailable. Moreover, it also helped to reveal the favored geometry for the enhancement of force effect. Later, the AFIR method was employed to study the mechanodegradation of generic polymers. The substituents effect and the polymer tacticity in strengthening the mechanical responsiveness, were highlighted by our study. Given the importance of cross-linker molecules in the double-network (DN) hydrogels, a fully automatic search of mechanochemical transformation pathways of a commonly used cross-linker molecule, N,N'-methylenebisacrylamide (MBAA), was also performed by the AFIR method. Through the work described in this article, we demonstrated that, in the field of polymer mechanochemistry, the AFIR method utilizing two forces is a simple but effective tool to give accurate predictions of activation force levels at any given timescale. In the meantime, the mechanistic study of mechanochemical reactions shown in this article is believed to provide insightful suggestions for the further design and application of mechanophores.

Cu(I)‐Catalyzed Enantioselective γ‐Boryl Substitution of Trifluoromethyl‐ and Silyl‐Substituted Alkenes
Natsuki Oyama; Sota Akiyama; Koji Kubota; Tsuneo Imamoto; Hajime Ito
European Journal of Organic Chemistry, 2022, 31, 159, 163, Wiley, 16 Aug. 2022, [Peer-reviewed], [Corresponding author]
Scientific journal

Mechanochemically Generated Calcium‐Based Heavy Grignard Reagents and Their Application to Carbon–Carbon Bond‐Forming Reactions
Pan Gao; Julong Jiang; Satoshi Maeda; Koji Kubota; Hajime Ito
Angewandte Chemie International Edition, 61, 41, e202207118, Wiley, 03 Aug. 2022, [Peer-reviewed], [Corresponding author]
Scientific journal

Stereospecific Synthesis of Silicon-Stereogenic Optically Active Silylboranes and their Application to Synthesis of Chiral Organosilanes
Xihong Wang; Chi Feng; Koji Kubota; Hajime Ito
American Chemical Society (ACS), 28 Jul. 2022, [Peer-reviewed], [Corresponding author]
Silylboranes have widespread applications in organic synthesis as versatile silylation reagents, which has inspired interest in studying methods for their synthesis. Silicon-stereogenic optically active silylboranes would allow the introduction of silicon-stereogenic silyl groups into various molecules. However, the synthesis of such silicon-stereogenic silylboranes remains unknown to date. Here, we report the first synthesis of silicon-stereogenic optically active silylboranes via stereospecific Pt(PPh3)4-catalyzed Si–H borylation of silicon-stereogenic hydrosilanes in high yield and perfect enantiospecificity (100% es) with retention of the configuration. Furthermore, the first characterization of silicon-stereogenic silyl-boranes by single crystal X-ray diffraction analysis was reported. This protocol is suitable for the stereospecific synthesis of silicon-stereogenic trialkyl-, dialkylbenzyl-, dialkylaryl-, and diarylalkyl-substituted silylboranes with excellent enantiomeric purity. The utility of the silicon-stereogenic silylboranes is demonstrated in silicon–silicon cross-coupling, transition-metal-catalyzed carbon–silicon bond-forming cross-coupling, and conjugate addition reactions with perfect enantiospecificity (100% es). The absolute configurations of the chiral silicon products were successfully confirmed by single-crystal X-ray diffraction analysis. The established synthetic strategy can be expected to expand the chemical space of silicon-stereogenic optically active organosilicon compounds with potentially interesting properties.

Palladium-catalyzed solid-state borylation of aryl halides using mechanochemistry
Koji Kubota; Emiru Baba; Tamae Seo; Tatsuo Ishiyama; Hajime Ito
Beilstein Journal of Organic Chemistry, 18, 855, 862, Beilstein Institut, 18 Jul. 2022, [Peer-reviewed], [Corresponding author]
Scientific journal, This study describes the solid-state palladium-catalyzed cross-coupling between aryl halides and bis(pinacolato)diboron using ball milling. The reactions were completed within 10 min for most aryl halides to afford a variety of synthetically useful arylboronates in high yields. Notably, all experimental operations could be performed in air, and did not require the use of large amounts of dry and degassed organic solvents. The utility of this method was further demonstrated by gram-scale synthesis under solvent-free, mechanochemical conditions.

Conformationally Fixed Chiral Bisphosphine Ligands by Steric Modulators on the Ligand Backbone: Selective Synthesis of Strained 1,2-Disubstituted Chiral cis-Cyclopropanes
Hiroaki Iwamoto; Yu Ozawa; Yuta Hayashi; Tsuneo Imamoto; Hajime Ito
Journal of the American Chemical Society, 144, 23, 10483, 10494, American Chemical Society (ACS), 07 Jun. 2022, [Peer-reviewed], [Corresponding author]
Scientific journal

Solid-state luminescence of Au(I) complexes with external stimuli-responsive properties
Mingoo Jin; Hajime Ito
Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 51, 100478, 100478, Elsevier {BV}, Jun. 2022, [Peer-reviewed], [Corresponding author]
Scientific journal

Insight into the Reactivity Profile of Solid-State Aryl Bromides in Suzuki–Miyaura Cross-Coupling Reactions Using Ball Milling
Koji Kubota; Hajime Ito; Keisuke Kondo; Tamae Seo
Synlett, Georg Thieme Verlag KG, 21 Jan. 2022, [Peer-reviewed], [Corresponding author]
English, Scientific journal, Despite recent advances in solid-state organic synthesis using ball milling, insight into the unique reactivity of solid-state substrates, which is often different from that in solution, has been poorly explored. In this study, we investigated the relationship between the reactivity and melting points of aryl halides in solid-state Suzuki–Miyaura cross-coupling reactions and the effect of reaction temperature on these processes. We found that aryl halides with high melting points showed significantly low reactivity in the solid-state cross-coupling near room temperature, but the reactions were notably accelerated by increasing the reaction temperature. Given that the reaction temperature is much lower than the melting points of these substrates, the acceleration effect is most likely ascribed to the weakening of the intermolecular interactions between the substrate molecules in the solid state. The present study provides important perspectives for the rational design of efficient solid-state organic transformations using ball milling.

Solid‐State C−N Cross‐Coupling Reactions with Carbazoles as Nitrogen Nucleophiles Using Mechanochemistry
Koji Kubota; Tsubura Endo; Minami Uesugi; Yuta Hayashi; Hajime Ito
ChemSusChem, 15, 2, e202102132, Wiley, 21 Jan. 2022, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Distinct Fold-Mode Formation of Crystalline Cu(I) Helical Coordination Polymers with Alternation of the Solid-State Emission Using Shape of the Counter Anions
Mingoo Jin; Rempei Ando; Hajime Ito
Inorganic Chemistry, 61, 9, 3, 9, American Chemical Society ({ACS}), 10 Jan. 2022, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Mechanical deformation and multiple thermal restoration of organic crystals: reversible multi-stage shape-changing effect with luminescence-color changes
Chi Feng; Tomohiro Seki; Shunichi Sakamoto; Toshiyuki Sasaki; Satoshi Takamizawa; Hajime Ito
Chemical Science, 13, 33, 9544, 9551, Royal Society of Chemistry (RSC), 2022, [Peer-reviewed], [Corresponding author]
Scientific journal, A reversible multi-stage shape-changing material based on an organic crystalline material is presented. Intriguingly, the interconversion among the three different shapes is accompanied by changes of the luminescence color.

Solid-state cross-coupling reactions of insoluble aryl halides under polymer-assisted grinding conditions
Koji Kubota; Tamae Seo; Hajime Ito
Faraday Discussions, Royal Society of Chemistry (RSC), 2022, [Peer-reviewed], [Corresponding author]
Scientific journal, In this study, polymer-assisted grinding (POLAG), a ball milling technique based on the use of polymer additives, was applied to mechanochemical solid-state Suzuki–Miyaura cross-coupling reactions of insoluble aryl halides. We...

Efficient access to materials-oriented aromatic alkynes via the mechanochemical Sonogashira coupling of solid aryl halides with large polycyclic conjugated systems
Yunpeng Gao; Chi Feng; Tamae Seo; Koji Kubota; Hajime Ito
Chemical Science, 13, 13, 430, 438, 2022, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Palladium-Catalyzed Solid-State Polyfluoroarylation of Aryl Halides Using Mechanochemistry
Rikuro Takahashi; Tamae Seo; Koji Kubota; Hajime Ito
ACS Catalysis, 11, 24, 14803, 14810, American Chemical Society ({ACS}), 17 Dec. 2021, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Mechanochemical synthesis of magnesium-based carbon nucleophiles in air and their use in organic synthesis
Rina Takahashi; Anqi Hu; Pan Gao; Yunpeng Gao; Yadong Pang; Tamae Seo; Julong Jiang; Satoshi Maeda; Hikaru Takaya; Koji Kubota; Hajime Ito
Nature Communications, 12, 1, 6691, Springer Science and Business Media {LLC}, 18 Nov. 2021, [Peer-reviewed], [Corresponding author]
English, Scientific journal, AbstractSince the discovery of Grignard reagents in 1900, the nucleophilic addition of magnesium-based carbon nucleophiles to various electrophiles has become one of the most powerful, versatile, and well-established methods for the formation of carbon−carbon bonds in organic synthesis. Grignard reagents are typically prepared via reactions between organic halides and magnesium metal in a solvent. However, this method usually requires the use of dry organic solvents, long reaction times, strict control of the reaction temperature, and inert-gas-line techniques. Despite the utility of Grignard reagents, these requirements still represent major drawbacks from both an environmental and an economic perspective, and often cause reproducibility problems. Here, we report the general mechanochemical synthesis of magnesium-based carbon nucleophiles (Grignard reagents in paste form) in air using a ball milling technique. These nucleophiles can be used directly for one-pot nucleophilic addition reactions with various electrophiles and nickel-catalyzed cross-coupling reactions under solvent-free conditions.

Regio- and Stereoselective Synthesis of Multi-Alkylated Allylic Boronates through Three-Component Coupling Reactions between Allenes, Alkyl Halides, and a Diboron Reagent
Yu Ozawa; Kohei Endo; Hajime Ito
Journal of the American Chemical Society, 143, 34, 13865, 13877, American Chemical Society ({ACS}), 01 Sep. 2021, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Correction to “General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis”
Ryosuke Shishido; Minami Uesugi; Rikuro Takahashi; Tsuyoshi Mita; Tatsuo Ishiyama; Koji Kubota; Hajime Ito
Journal of the American Chemical Society, 143, 33, 13460, 13460, American Chemical Society ({ACS}), 25 Aug. 2021, [Peer-reviewed], [Corresponding author]
Scientific journal

Single Crystal Growth of π-Conjugated Large Molecules without Solubilizing Alkyl Chains via the Naphthalene Flux Method
Takashi Yanase; Hirohiko Tanoguchi; Nobuhiko Sakai; Mingoo Jin; Ichiro Yamane; Masaki Kato; Hajime Ito; Taro Nagahama; Toshihiro Shimada
Crystal Growth & Design, American Chemical Society ({ACS}), 04 Aug. 2021, [Peer-reviewed], [Corresponding author]
Scientific journal

Charge-transfer crystal with segregated packing structure constructed with hexaarylbenzene and tetracyanoquinodimethane
Rempei Ando; Mingoo Jin; Hajime Ito
CRYSTENGCOMM, 23, 5564, 5568, Aug. 2021, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Cover Picture: Introduction of a Luminophore into Generic Polymers via Mechanoradical Coupling with a Prefluorescent Reagent (Angew. Chem. Int. Ed. 29/2021)
Koji Kubota; Naoki Toyoshima; Daiyo Miura; Julong Jiang; Satoshi Maeda; Mingoo Jin; Hajime Ito
Angewandte Chemie International Edition, 60, 29, 15661, 15661, Wiley, 12 Jul. 2021, [Peer-reviewed], [Corresponding author]
Scientific journal

Introduction of a Luminophore into Generic Polymers via Mechanoradical Coupling with a Prefluorescent Reagent
Koji Kubota; Naoki Toyoshima; Daiyo Miura; Julong Jiang; Satoshi Maeda; Mingoo Jin; Hajime Ito
Angewandte Chemie, 133, 29, 16139, 16144, Wiley, 12 Jul. 2021, [Peer-reviewed], [Corresponding author]
Scientific journal

Titelbild: Introduction of a Luminophore into Generic Polymers via Mechanoradical Coupling with a Prefluorescent Reagent (Angew. Chem. 29/2021)
Koji Kubota; Naoki Toyoshima; Daiyo Miura; Julong Jiang; Satoshi Maeda; Mingoo Jin; Hajime Ito
Angewandte Chemie, 133, 29, 15793, 15793, Wiley, 12 Jul. 2021, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Introduction of a Luminophore into Generic Polymers via Mechanoradical Coupling with a Prefluorescent Reagent
Koji Kubota; Naoki Toyoshima; Daiyo Miura; Julong Jiang; Satoshi Maeda; Mingoo Jin; Hajime Ito
Angewandte Chemie International Edition, 60, 29, 16003, 16008, Wiley, 12 Jul. 2021, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Synthesis of Chiral α-Amino Tertiary Boronates via the Catalytic Enantioselective Nucleophilic Borylation of Dialkyl Ketimines
Koji Kubota; Daiyo Miura; Takumi Takeuchi; Shun Osaki; Hajime Ito
ACS Catalysis, 11, 11, 6733, 6740, American Chemical Society ({ACS}), 04 Jun. 2021, [Peer-reviewed], [Corresponding author]
Scientific journal

Synthesis and Optical Properties of C,N-Swapped Boranils Derived from Potassium Acyltrifluoroborates
Satsuki Matsuura; Jumpei Taguchi; Tomohiro Seki; Hajime Ito
Bulletin of the Chemical Society of Japan, 94, 5, 1547, 1552, The Chemical Society of Japan, 15 May 2021, [Peer-reviewed], [Corresponding author]
Scientific journal

Backbone-Modified C2-Symmetrical Chiral Bisphosphine TMS-QuinoxP*: Asymmetric Borylation of Racemic Allyl Electrophiles
Hiroaki Iwamoto; Yu Ozawa; Yuta Takenouchi; Tsuneo Imamoto; Hajime Ito
Journal of the American Chemical Society, 143, 17, 6413, 6422, American Chemical Society ({ACS}), 05 May 2021, [Peer-reviewed], [Corresponding author]
Scientific journal

Tackling Solubility Issues in Organic Synthesis: Solid-State Cross-Coupling of Insoluble Aryl Halides
Tamae Seo; Naoki Toyoshima; Koji Kubota; Hajime Ito
Journal of the American Chemical Society, American Chemical Society ({ACS}), 28 Apr. 2021, [Peer-reviewed], [Corresponding author], [International Magazine]
English, Scientific journal, Conventional organic synthesis generally relies on the use of liquid organic solvents to dissolve the reactants. Therefore, reactions of sparingly soluble or insoluble substrates are challenging and often ineffective. The development of a solvent-independent solid-state approach that overcomes this longstanding solubility issue would provide innovative synthetic solutions and access to new areas of chemical space. Here, we report extremely fast and highly efficient solid-state palladium-catalyzed Suzuki-Miyaura cross-coupling reactions via a high-temperature ball-milling technique. This solid-state protocol enables the highly efficient cross-couplings of insoluble aryl halides with large polyaromatic structures that are barely reactive under conventional solution-based conditions. Notably, we discovered a new luminescent organic material with a strong red emission. This material was prepared via the solid-state coupling of Pigment violet 23, a compound that has so far not been involved in molecular transformations due to its extremely low solubility. This study thus provides a practical method for accessing unexplored areas of chemical space through molecular transformations of insoluble organic compounds that cannot be carried out by any other approach.

(9-Isocyanoanthracene)gold(I) Complexes Exhibiting Two Modes of Crystal Jumps by Different Structure Change Mechanisms
Kenta Kato; Tomohiro Seki; Hajime Ito
Inorganic Chemistry, American Chemical Society (ACS), 22 Apr. 2021, [Peer-reviewed], [Corresponding author]
Scientific journal

A Copper(I)-Catalyzed Radical-Relay Reaction Enabling the Intermolecular 1,2-Alkylborylation of Unactivated Olefins
Sota Akiyama; Natsuki Oyama; Tsubura Endo; Koji Kubota; Hajime Ito
Journal of the American Chemical Society, 143, 13, 5260, 5268, American Chemical Society ({ACS}), 07 Apr. 2021, [Peer-reviewed], [Corresponding author], [International Magazine]
English, Scientific journal, The first catalytic intermolecular 1,2-alkylborylation reaction via a radical-relay mechanism between unactivated olefins, bis(pinacolato)diboron, and an alkyl electrophile is reported. Successful implementation of this method requires that the competing boryl substitution of the alkyl electrophile is retarded to facilitate the radical relay. This challenge was overcome using electronically or sterically demanding alkyl electrophiles, which results in the simultaneous and highly regioselective introduction of a gem-difluoro, monofluoro, tertiary, or secondary alkyl group and a boryl group across the C═C double bond.

Encapsulating N-Heterocyclic Carbene Binuclear Transition-Metal Complexes as a New Platform for Molecular Rotation in Crystalline Solid-State
Mingoo Jin; Rempei Ando; Marcus J. Jellen; Miguel A. Garcia-Garibay; Hajime Ito
Journal of the American Chemical Society, American Chemical Society ({ACS}), 20 Jan. 2021, [Peer-reviewed], [Corresponding author], [International Magazine]
English, Scientific journal, In crystalline solids, molecules generally have limited mobility due to their densely packed environment. However, structural information at the molecular level may be used to design amphidynamic crystals with rotating elements linked to rigid, lattice-forming parts, which may lead to molecular rotary motions and changes in conformation that determine the physical properties of the solid-state materials. Here, we report a novel design of emissive crystalline molecular rotors with a central pyrazine rotator connected by implanted transition metals (Cu or Au) to a readily accessible enclosure formed by two N-heterocyclic carbenes (NHC) in discrete binuclear complexes. The activation energies for the rotation could be tuned by changing the implanted metal. Exchanging Cu to Au resulted in an ∼4.0 kcal/mol reduction in the rotational energy barrier as a result of lower steric demand by elongation of the axle with the noble metal, and a stronger electronic stabilization in the rotational transition state by enhancement of the d-π* interactions between the metal centers and the pyrazine rotator. The Cu(I) rotor complex showed a greater electronic delocalization than the Au(I) rotor complex, causing a red-shifted solid-state emission. Molecular rotation-induced emission quenching was observed in both crystals. The enclosing NHC rotors are easy to prepare, and their rotational motion should be less dependent on packing structures, which are often crucial for many previously documented amphidynamic molecular crystals. The platform from the encapsulating NHC cationic metal complexes and the metal-centered rotation-axis provide a promising scaffold for a novel design of crystalline molecular rotors, including manipulation of rotary dynamics and solid-state emission.

Synthesis of hydrosilylboronates via the monoborylation of a dihydrosilane Si−H bond and their application for the generation of dialkylhydrosilyl anions
Takumi Takeuchi; Ryosuke Shishido; Koji Kubota; Hajime Ito
Chemical Science, 12, 11799, 11804, Royal Society of Chemistry (RSC), 2021, [Peer-reviewed], [Corresponding author]
English, Scientific journal,

The synthesis of a series of hydrosilylboronates via the selective iridium- or nickel-catalyzed monoborylation of dihydrosilane Si−H bonds is described. The synthesized silylboronates, which bear a single Si−H bond, can...

Solid‐State Radical C−H Trifluoromethylation Reactions Using Ball Milling and Piezoelectric Materials
Yadong Pang; Joo Won Lee; Koji Kubota; Hajime Ito
Angewandte Chemie International Edition, 59, 50, 22570, 22576, Wiley, 07 Dec. 2020, [Peer-reviewed], [Corresponding author]
Scientific journal

Stacked nanocarbon photosensitizer for efficient blue light excited Eu(III) emission
Yuichi Kitagawa; Fumiya Suzue; Takayuki Nakanishi; Koji Fushimi; Tomohiro Seki; Hajime Ito; Yasuchika Hasegawa
Communications Chemistry, 3, 1, 01 Dec. 2020, [Peer-reviewed], [Corresponding author]
Scientific journal

Copper(I)-catalyzed Stereoselective Silylative Dearomatization of Indoles and Pyrroles Using Silylboronates
Keiichi Hayama; Rikuro Takahashi; Koji Kubota; Hajime Ito
Chemistry Letters, 50, 2, 289, 292, Oxford University Press (OUP), 11 Nov. 2020
Scientific journal, Abstract

Silylative dearomatizations of indole-2-carboxylates were accomplished using a copper(I) catalyst and silylboronates. This reaction presumably proceeds through regioselective addition of silylcopper(I) species to indole substrates followed by highly diastereoselective protonation of the resulting copper(I) enolate intermediates to afford the corresponding dearomative silylation products. The first silylative dearomatization of pyrroles using the developed catalytic system is also described.

A Glove-Box- and Schlenk-Line-Free Protocol for Solid-State C–N Cross-Coupling Reactions Using Mechanochemistry
Koji Kubota; Rikuro Takahashi; Minami Uesugi; Hajime Ito
ACS Sustainable Chemistry & Engineering, 8, 44, 16577, 16582, 09 Nov. 2020, [Peer-reviewed], [Corresponding author]
English, Scientific journal

General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis
Ryosuke Shishido; Minami Uesugi; Rikuro Takahashi; Tsuyoshi Mita; Tatsuo Ishiyama; Koji Kubota; Hajime Ito
Journal of the American Chemical Society, 142, 33, 14125, 14133, American Chemical Society ({ACS}), 19 Aug. 2020, [Peer-reviewed], [Corresponding author]
Scientific journal

Thermosalience in Macrocycle-Based Soft Crystals via Anisotropic Deformation of Disilanyl Architecture
Kenichiro Omoto; Toyotaka Nakae; Masaki Nishio; Yoshinori Yamanoi; Hidetaka Kasai; Eiji Nishibori; Takaki Mashimo; Tomohiro Seki; Hajime Ito; Kazuki Nakamura; Norihisa Kobayashi; Naofumi Nakayama; Hitoshi Goto; Hiroshi Nishihara
Journal of the American Chemical Society, American Chemical Society ({ACS}), 22 Jul. 2020, [Peer-reviewed], [Corresponding author]
Scientific journal

Selective Mechanochemical Monoarylation of Unbiased Dibromoarenes by in Situ Crystallization
Tamae Seo; Koji Kubota; Hajime Ito
Journal of the American Chemical Society, 142, 22, 9884, 9889, 03 Jun. 2020, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Photoluminescent Ferroelastic Molecular Crystals
Tomohiro Seki; Chi Feng; Kentaro Kashiyama; Shunichi Sakamoto; Yuichi Takasaki; Toshiyuki Sasaki; Satoshi Takamizawa; Hajime Ito
Angewandte Chemie, 132, 23, 8924, 8928, Wiley, 02 Jun. 2020, [Peer-reviewed], [Corresponding author]
Scientific journal

Photoluminescent Ferroelastic Molecular Crystals
Tomohiro Seki; Chi Feng; Kentaro Kashiyama; Shunichi Sakamoto; Yuichi Takasaki; Toshiyuki Sasaki; Satoshi Takamizawa; Hajime Ito
Angewandte Chemie International Edition, 59, 23, 8839, 8843, 02 Jun. 2020, [Peer-reviewed], [Corresponding author], [International Magazine]
English, Scientific journal

Copper(I)-Catalyzed Boryl Substitution of 1-Trifluoromethyl Allenes for the Synthesis of 3-Boryl-Substituted 1,1-gem-Difluorodienes
Sota Akiyama; Syogo Nomura; Koji Kubota; Hajime Ito
The Journal of Organic Chemistry, 85, 6, 4172, 4181, American Chemical Society ({ACS}), 20 Mar. 2020, [Peer-reviewed], [Corresponding author]
Scientific journal

Synthesis and Tunable Optical Properties of C,N‐Chelated Borate Luminophores Derived from Potassium Acyltrifluoroborates
Jumpei Taguchi; Satsuki Matsuura; Tomohiro Seki; Hajime Ito
Chemistry – A European Journal, 26, 11, 2450, 2455, 21 Feb. 2020, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Silyl-Group-Directed Linear-Selective Allylation of Carbonyl Compounds with Trisubstituted Allylboronates Using a Copper(I) Catalyst
Hiroaki Iwamoto; Yuta Hayashi; Yu Ozawa; Hajime Ito
ACS Catalysis, 2471, 2476, American Chemical Society ({ACS}), 21 Feb. 2020, [Peer-reviewed], [Corresponding author]
Scientific journal

Crystal Jumping of Simple Hydrocarbons: Cooling-induced Salient Effect of Bis-, Tri-, and Tetraphenylethene through Anisotropic Lattice Dimension Changes without Thermal Phase Transitions
Tomohiro Seki; Takaki Mashimo; Hajime Ito
CHEMISTRY LETTERS, 49, 2, 174, 177, Feb. 2020, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Synthesis of Chiral N-Heterocyclic Allylboronates via the Enantioselective Borylative Dearomatization of Pyrroles
Keiichi Hayama; Ryoto Kojima; Koji Kubota; Hajime Ito
Organic Letters, American Chemical Society ({ACS}), 17 Jan. 2020, [Peer-reviewed], [Corresponding author]
Scientific journal

Aurophilicity‐Mediated Construction of Emissive Porous Molecular Crystals as Versatile Hosts for Liquid and Solid Guests
Tomohiro Seki; Kentaro Ida; Hiroyasu Sato; Shinji Aono; Shigeyoshi Sakaki; Hajime Ito
Chemistry – A European Journal, 26, 3, 735, 744, 13 Jan. 2020, [Peer-reviewed], [Corresponding author]
English, Scientific journal

8 Borylative Ring Closing
K. Kubota; H. Ito
Georg Thieme Verlag, 2020, [Peer-reviewed], [Corresponding author]

Mixed crystal formation of two gold isocyanide complexes with various ratios for continuous tuning of photophysical properties
Tomohiro Seki; Naoki Toyoshima; Hajime Ito
Dalton Transactions, 49, 7, 2073, 2076, 2020, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Air- and moisture-stable Xantphos-ligated palladium dialkyl complex as a precatalyst for cross-coupling reactions
Rina Takahashi; Koji Kubota; Hajime Ito
Chemical Communications, Royal Society of Chemistry ({RSC}), 2020, [Peer-reviewed], [Corresponding author]
Scientific journal

Redox reactions of small organic molecules using ball milling and piezoelectric materials
Hajime Ito; Koji Kubota; Yadong Pang; Akira Miura; Hajime Ito
Science, 366, 6472, 1500, 1504, American Association for the Advancement of Science ({AAAS}), 20 Dec. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Catalytic generation of silicon nucleophiles
Koji Kubota; Hajime Ito
Organosilicon Chemistry: Novel Approaches and Reactions, 1, 31, wiley, 10 Dec. 2019, [Peer-reviewed], [Corresponding author]
English, In book

Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals
Hajime Ito; Mingoo Jin; Sho Yamamoto; Tomohiro Seki; Hajime Ito; Miguel A. Garcia‐Garibay
Angewandte Chemie, 131, 50, 18171, 18178, Wiley, 09 Dec. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals
Hajime Ito; Mingoo Jin; Sho Yamamoto; Tomohiro Seki; Hajime Ito; Miguel A. Garcia-Garibay
Angewandte Chemie International Edition, 58, 50, 18003, 18010, Wiley, 09 Dec. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Olefin-accelerated solid-state C–N cross-coupling reactions using mechanochemistry
Hajime Ito; Koji Kubota; Tamae Seo; Katsumasa Koide; Yasuchika Hasegawa; Hajime Ito
Nature Communications, 10, 1, Dec. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Direct Dimesitylborylation of Benzofuran Derivatives by an Iridium‐Catalyzed C−H Activation with Silyldimesitylborane
Hajime Ito; Ryosuke Shishido; Ikuo Sasaki; Tomohiro Seki; Tatsuo Ishiyama; Hajime Ito
Chemistry – A European Journal, 25, 56, 12924, 12928, Wiley, 08 Oct. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Near-IR Luminescent Yb^III Coordination Polymers Composed of Pyrene Derivatives for Thermostable Oxygen Sensors
Yasuchika Hasegawa; Takafumi Matsui; Yuichi Kitagawa; Takayuki Nakanishi; Tomohiro Seki; Hajime Ito; Yuta Nakasaka; Takao Masuda; Koji Fushimi
Chemistry - A European Journal, 25, 53, 12308, 12315, 20 Sep. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Frontispiz: Catalytic Enantioselective Synthesis of Allylic Boronates Bearing a Trisubstituted Alkenyl Fluoride and Related Derivatives
Sota Akiyama; Koji Kubota; Malte S. Mikus; Paulo H. S. Paioti; Filippo Romiti; Qinghe Liu; Yuebiao Zhou; Amir H. Hoveyda; Hajime Ito
Angewandte Chemie, 131, 35, Wiley, 26 Aug. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Catalytic Enantioselective Synthesis of Allylic Boronates Bearing a Trisubstituted Alkenyl Fluoride and Related Derivatives
Hajime Ito; Sota Akiyama; Koji Kubota; Malte S. Mikus; Paulo H. S. Paioti; Filippo Romiti; Qinghe Liu; Yuebiao Zhou; Amir H. Hoveyda; Hajime Ito
Angewandte Chemie International Edition, 58, 35, 11998, 12003, 26 Aug. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Copper(I)-Catalyzed Enantioconvergent Borylation of Racemic Benzyl Chlorides Enabled by Quadrant-by-Quadrant Structure Modification of Chiral Bisphosphine Ligands
Hajime Ito; Hiroaki Iwamoto; Kohei Endo; Yu Ozawa; Yuta Watanabe; Koji Kubota; Tsuneo Imamoto; Hajime Ito
Angewandte Chemie International Edition, 58, 32, 11112, 11117, Wiley, 05 Aug. 2019, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Inside Cover: Concise Synthesis of Potassium Acyltrifluoroborates from Aldehydes through Copper(I)-Catalyzed Borylation/Oxidation (Angew. Chem. Int. Ed. 22/2019)
Hajime Ito; Jumpei Taguchi; Takumi Takeuchi; Rina Takahashi; Fabio Masero; Hajime Ito
Angewandte Chemie International Edition, 58, 22, 7146, 7146, Wiley, 27 May 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Concise Synthesis of Potassium Acyltrifluoroborates from Aldehydes through Copper(I)-Catalyzed Borylation/Oxidation
Hajime Ito; Jumpei Taguchi; Takumi Takeuchi; Rina Takahashi; Fabio Masero; Hajime Ito
Angewandte Chemie International Edition, 58, 22, 7299, 7303, 27 May 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Soft Crystals: Flexible Response Systems with High Structural Order
Hajime Ito; Masako Kato; Hajime Ito; Miki Hasegawa; Kazuyuki Ishii
Chemistry – A European Journal, 25, 20, 5105, 5112, 05 Apr. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Cover Feature: Iridium(I)‐Catalyzed C−H Borylation in Air by Using Mechanochemistry (Chem. Eur. J. 18/2019)
Yadong Pang; Tatsuo Ishiyama; Koji Kubota; Hajime Ito
Chemistry – A European Journal, 25, 18, 4532, 4532, Wiley, 27 Mar. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Iridium(I)‐Catalyzed C−H Borylation in Air by Using Mechanochemistry
Hajime Ito; Yadong Pang; Tatsuo Ishiyama; Koji Kubota; Hajime Ito
Chemistry – A European Journal, 25, 18, 4654, 4659, 27 Mar. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Microphase separation of carbohydrate-based star-block copolymers with sub-10 nm periodicity
Takuya Isono; Nao Kawakami; Kodai Watanabe; Kohei Yoshida; Issei Otsuka; Hiroaki Mamiya; Hajime Ito; Takuya Yamamoto; Kenji Tajima; Redouane Borsali; Toshifumi Satoh
Polymer Chemistry, 10, 9, 1119, 1129, 07 Mar. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Dependence of Absorption and Emission Spectra on Polymorphs of Gold(I) Isocyanide Complexes: Theoretical Study with QM/MM Approach
Hajime Ito; Shinji Aono; Tomohiro Seki; Hajime Ito; Shigeyoshi Sakaki
The Journal of Physical Chemistry C, 123, 8, 4773, 4794, 28 Feb. 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

The Direct Dimesitylborylation of Benzofuran Derivatives via an Iridium-Catalyzed C–H Activation with Silyldimesitylborane
Ryosuke Shishido; Ikuo Sasaki; Tomohiro Seki; Tatsuo Ishiyama; Hajime Ito
Chem. Eur. J. (IF:5.16) Just Accepted, 2019, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Solid-state Suzuki–Miyaura cross-coupling reactions: olefin-accelerated C–C coupling using mechanochemistry
Hajime Ito; Tamae Seo; Tatsuo Ishiyama; Koji Kubota; Hajime Ito
Chemical Science, 10, 35, 8202, 8210, Royal Society of Chemistry ({RSC}), 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Luminescent mechanochromism of gold N-heterocyclic carbene complexes with hypso- and bathochromic spectral shifts
Hajime Ito; Tomohiro Seki; Kentaro Kashiyama; Hajime Ito
Dalton Transactions, 48, 21, 7105, 7109, 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Anisotropic strain release in a thermosalient crystal: correlation between the microscopic orientation of molecular rearrangements and the macroscopic mechanical motion
Hajime Ito; Tomohiro Seki; Takaki Mashimo; Hajime Ito
Chemical Science, 10, 15, 4185, 4191, 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Synthesis of 2-alkyl-2-boryl-substituted-tetrahydrofurans via copper(i)-catalysed borylative cyclization of aliphatic ketones
Hajime Ito; Koji Kubota; Minami Uesugi; Shun Osaki; Hajime Ito
Organic & Biomolecular Chemistry, 17, 23, 5680, 5683, 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

Mechanochemistry allows carrying out sensitive organometallic reactions in air: glove-box-and-Schlenk-line-free synthesis of oxidative addition complexes from aryl halides and palladium(0)
Hajime Ito; Koji Kubota; Rina Takahashi; Hajime Ito
Chemical Science, 10, 22, 5837, 5842, 2019, [Peer-reviewed], [Corresponding author]
Scientific journal

A gold isocyanide complex with a pendant carboxy group: orthogonal molecular arrangements and hypsochromically shifted luminescent mechanochromism (vol 54, pg 11136, 2018)
Seki Tomohiro; Kobayashi Koh; Mashimo Takaki; Ito Hajime
CHEMICAL COMMUNICATIONS, 54, 93, 13160, 04 Dec. 2018, [Peer-reviewed], [Corresponding author]

Structural Manipulation of Triboluminescent Lanthanide Coordination Polymers by Side-Group Alteration
Hajime Ito; Yuichi Hirai; Pedro Paulo Ferreira da Rosa; Takayuki Nakanishi; Yuichi Kitagawa; Koji Fushimi; Tomohiro Seki; Hajime Ito; Yasuchika Hasegawa
Inorganic Chemistry, 57, 23, 14653, 14659, 03 Dec. 2018, [Peer-reviewed], [Corresponding author]
Scientific journal

Synthesis and Evaluation of a 1,3a,6a-Triazapentalene (TAP)-Bonded System
Ito Masami; Mera Akane; Mashimo Takaki; Seki Tomohiro; Karanjit Sangita; Ohashi Eisaku; Nakayama Atsushi; Kitamura Kei; Hamura Toshiyuki; Ito Hajime; Namba Kosuke
CHEMISTRY-A EUROPEAN JOURNAL, 24, 67, 17727, 17733, 03 Dec. 2018, [Peer-reviewed], [Corresponding author]

Computational design of high-performance ligand for enantioselective Markovnikov hydroboration of aliphatic terminal alkenes
Hiroaki Iwamoto; Tsuneo Imamoto; Hajime Ito
Nature Communications, 9, 1, Dec. 2018, [Peer-reviewed], [Corresponding author]
Scientific journal

Copper(I)-catalyzed Stereoselective Defluoroborylation of Aliphatic Gem-Difluoroalkenes
Ito Hajime; Seo Tamae; Kojima Ryoto; Kubota Koji
CHEMISTRY LETTERS, 47, 10, 1330, 1332, Oct. 2018, [Peer-reviewed], [Corresponding author]

Spiral Eu(iii) coordination polymers with circularly polarized luminescence
Yasuchika Hasegawa; Yui Miura; Yuichi Kitagawa; Satoshi Wada; Takayuki Nakanishi; Koji Fushimi; Tomohiro Seki; Hajime Ito; Takeshi Iwasa; Tetsuya Taketsugu; Masayuki Gon; Kazuo Tanaka; Yoshiki Chujo; Shingo Hattori; Masanobu Karasawa; Kazuyuki Ishii
Chemical Communications, 54, 76, 10695, 10697, 28 Sep. 2018, [Peer-reviewed], [Corresponding author]
Scientific journal

Copper(i)-catalysed stereoselective debromoborylation of aliphatic 1,1-dibromo-1-alkenes with bis(pinacolato)diboron
Yadong Pang; Ryoto Kojima; Hajime Ito
Organic & Biomolecular Chemistry, 16, 34, 6187, 6190, 14 Sep. 2018, [Peer-reviewed], [Corresponding author]
Scientific journal

Spin-orbit coupling dependent energy transfer in luminescent nonanuclear Yb-Gd / Yb-Lu clusters
Shun Omagari; Takayuki Nakanishi; Yuichi Kitagawa; Tomohiro Seki; Koji Fushimi; Hajime Ito; Andries Meijerink; Yasuchika Hasegawa
Journal of Luminescence, 201, 170, 175, Sep. 2018, [Peer-reviewed], [Corresponding author]
Scientific journal

Copper(I)-catalyzed regio- and diastereoselective intramolecular alkylboration of terminal allenes
Ozawa Yu; Iwamoto Hiroaki; Ito Hajime
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 256, 19 Aug. 2018, [Peer-reviewed], [Corresponding author]
English

Synthesis of alpha-amino acylboron bearing hydroxylamine moiety for preparation of peptides bearing acylboron moiety
Takahashi Rina; Taguchi Jumpei; Bode Jeffery; Ito Hajime
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 256, 19 Aug. 2018, [Peer-reviewed], [Corresponding author]

Ultra-High-Resolution Computed Tomography Angiography for Assessment of Coronary Artery Stenosis
Motoyama Sadako; Ito Hajime; Sarai Masayoshi; Nagahara Yasuomi; Miyajima Keiichi; Matsumoto Ryota; Doi Yujiro; Kataoka Yumi; Takahashi Hiroshi; Ozaki Yukio; Toyama Hiroshi; Katada Kazuhiro
CIRCULATION JOURNAL, 82, 7, 1844, 1851, Jul. 2018, [Peer-reviewed], [Corresponding author]

A Copper(I)-Catalyzed Enantioselective γ-Boryl Substitution of Trifluoromethyl-Substituted Alkenes: Synthesis of Enantioenriched γ,γ-gem-Difluoroallylboronates
Ryoto Kojima; Sota Akiyama; Hajime Ito
Angewandte Chemie - International Edition, 57, 24, 7196, 7199, 11 Jun. 2018, [Peer-reviewed], [Corresponding author]
English, Scientific journal

A meta-diisocyanide benzene-based aryl gold isocyanide complex exhibiting multiple solid-state molecular arrangements and luminescent mechanochromism
Tomohiro Seki; Kentaro Ida; Hajime Ito
Materials Chemistry Frontiers, 2, 6, 1195, 1200, 01 Jun. 2018, [Peer-reviewed], [Corresponding author]
Scientific journal

Thermosensitive Seven-Coordinate TbIII Complexes with LLCT Transitions
Pedro Paulo Ferreira da Rosa; Takayuki Nakanishi; Yuichi Kitagawa; Tomohiro Seki; Hajime Ito; Koji Fushimi; Yasuchika Hasegawa
European Journal of Inorganic Chemistry, 2018, 19, 2031, 2037, 24 May 2018, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper-catalyzed asymmetric dearomative borylation: New pathway to optically active heterocyclic compounds
Hajime Ito
Pure and Applied Chemistry, 90, 4, 703, 710, 28 Mar. 2018, [Peer-reviewed], [Corresponding author]
English, International conference proceedings

Mechanical-Stimulation-Triggered and Solvent-Vapor-Induced Reverse Single-Crystal-to-Single-Crystal Phase Transitions with Alterations of the Luminescence Color
Mingoo Jin; Toshiki Sumitani; Hiroyasu Sato; Tomohiro Seki; Hajime Ito
Journal of the American Chemical Society, 140, 8, 2875, 2879, 28 Feb. 2018, [Peer-reviewed], [Corresponding author]
English, Scientific journal

A Luminescent Dinuclear EuIII/TbIII Complex with LMCT Band as a Single-Molecular Thermosensor
Kei Yanagisawa; Yuichi Kitagawa; Takayuki Nakanishi; Tomohiro Seki; Koji Fushimi; Hajime Ito; Yasuchika Hasegawa
Chemistry - A European Journal, 24, 8, 1956, 1961, 06 Feb. 2018, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Origin of Concentration Quenching in Ytterbium Coordination Polymers: Phonon-Assisted Energy Transfer
Shun Omagari; Takayuki Nakanishi; Yuichi Hirai; Yuichi Kitagawa; Tomohiro Seki; Koji Fushimi; Hajime Ito; Yasuchika Hasegawa
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 5, 561, 567, Feb. 2018, [Peer-reviewed], [Corresponding author]
English, Scientific journal

A gold isocyanide complex with a pendant carboxy group: orthogonal molecular arrangements and hypsochromically shifted luminescent mechanochromism
Tomohiro Seki; Koh Kobayashi; Takaki Mashimo; Hajime Ito
Chemical Communications, 54, 79, 11136, 11139, Royal Society of Chemistry ({RSC}), 2018, [Peer-reviewed], [Corresponding author]
Scientific journal

Copper(i)-catalysed regio- and diastereoselective intramolecular alkylboration of terminal allenes via allylcopper(i) isomerization
Yu Ozawa; Hiroaki Iwamoto; Hajime Ito
Chemical Communications, 54, 39, 4991, 4994, 2018, [Peer-reviewed], [Corresponding author]
Scientific journal

Synthesis and photophysical properties of Eu(III) complexes with phosphine oxide ligands including metal ions
Masanori Yamamoto; Takayuki Nakanishi; Yuichi Kitagawa; Tomohiro Seki; Hajime Ito; Koji Fushimi; Yasuchika Hasegawa
Bulletin of the Chemical Society of Japan, 91, 1, 6, 11, 2018, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Soft Crystal Force Field for Reproducing the Crystal Structures of Aryl Gold Isocyanide Complexes
Nakayama Naofumi; Obata Shigeaki; Hori Yoshikazu; Goto Hitoshi; Seki Tomohiro; Ito Hajime
JOURNAL OF COMPUTER CHEMISTRY-JAPAN, 17, 3, 155, 157, 2018, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Phosphorescence Control Mediated by Molecular Rotation and Aurophilic Interactions in Amphidynamic Crystals of 1,4-Bis[tri-(p-fluorophenyl)phosphane-gold(I)-ethynyl]benzene
Mingoo Jin; Tim S. Chung; Tomohiro Seki; Hajime Ito; Miguel A. Garcia-Garibay
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 139, 49, 18115, 18121, Dec. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-catalyzed Diastereoselective Dearomative Carboborylation of Indoles
Keiichi Hayama; Koji Kubota; Hiroaki Iwamoto; Hajime Ito
CHEMISTRY LETTERS, 46, 12, 1800, 1802, Dec. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-Catalyzed Boryl Substitution of Allyl Aminals: Selective Synthesis of Linear gamma-Aminoallylboronates
Yuta Takenouchi; Hajime Ito
SYNTHESIS-STUTTGART, 49, 21, 4738, 4744, Nov. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Formal Nucleophilic Silyl Substitution of Aryl Halides with Silyllithium Reagents via Halogenophilic Attack of Silyl Nucleophiles
Eiji Yamamoto; Satoshi Ukigai; Hajime Ito
SYNLETT, 28, 18, 2460, 2464, Nov. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Synthesis of Acylborons by Ozonolysis of Alkenylboronates: Preparation of an Enantioenriched Amino Acid Acylboronate
Jumpei Taguchi; Toshiki Ikeda; Rina Takahashi; Ikuo Sasaki; Yasushi Ogasawara; Tohru Dairi; Naoya Kato; Yasunori Yamamoto; Jeffrey W. Bode; Hajime Ito
Angewandte Chemie, 129, 44, 14035, 14039, Wiley-Blackwell, 23 Oct. 2017, [Peer-reviewed], [Corresponding author]
Scientific journal

Stereodivergent hydrodefluorination of gem-difluoroalkenes: selective synthesis of (Z)- and (E)-monofluoroalkenes
Ryoto Kojima; Koji Kubota; Hajime Ito
CHEMICAL COMMUNICATIONS, 53, 77, 10688, 10691, Oct. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-Catalyzed Regio- and Stereoselective Intramolecular Alkylboration of Propargyl Ethers and Amines
Hiroaki Iwamoto; Yu Ozawa; Koji Kubota; Hajime Ito
JOURNAL OF ORGANIC CHEMISTRY, 82, 19, 10563, 10573, Oct. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Synthesis of Acylborons by Ozonolysis of Alkenylboronates: Preparation of an Enantioenriched Amino Acid Acylboronate
Jumpei Taguchi; Toshiki Ikeda; Rina Takahashi; Ikuo Sasaki; Yasushi Ogasawara; Tohru Dairi; Naoya Kato; Yasunori Yamamoto; Jeffrey W. Bode; Hajime Ito
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 56, 44, 13847, 13851, Oct. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Tuning the Lifetime of Transient Phases of Mechanochromic Gold Isocyanide Complexes through Functionalization of the Terminal Moieties of Flexible Side Chains
Tomohiro Seki; Kentaro Kashiyama; Shiki Yagai; Hajime Ito
Chemistry Letters, 46, 9, 1415, 1418, The Chemical Society of Japan, 05 Sep. 2017, [Peer-reviewed], [Corresponding author]
Scientific journal

Enhanced Luminescence of Asymmetrical Seven-Coordinate Eu-III Complexes Including LMCT Perturbation
Kei Yanagisawa; Yuichi Kitagawa; Takayuki Nakanishi; Tomoko Akama; Masato Kobayashi; Tomohiro Seki; Koji Fushimi; Hajime Ito; Tetsuya Taketsugu; Yasuchika Hasegawa
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 32, 3843, 3848, Sep. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Tris(trimethylsilyl)silylboronate Esters: Novel Bulky, Air- and Moisture-Stable Silylboronate Ester Reagents for Boryl Substitution and Silaboration Reactions
Eiji Yamamoto; Ryosuke Shishido; Tomohiro Seki; Hajime Ito
ORGANOMETALLICS, 36, 16, 3019, 3022, Aug. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Transition-Metal-Free Boryl Substitution Using Silylboranes and Alkoxy Bases
Eiji Yamamoto; Satoshi Maedab; Tetsuya Taketsugub; Hajime Ito
SYNLETT, 28, 11, 1258, 1267, Jul. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Triboluminescence of Lanthanide Coordination Polymers with Face-to-Face Arranged Substituents
Yuichi Hirai; Takayuki Nakanishi; Yuichi Kitagawa; Koji Fushimi; Tomohiro Seki; Hajime Ito; Yasuchika Hasegawa
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 56, 25, 7171, 7175, Jun. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)‐Catalyzed Enantioselective Nucleophilic Borylation of Aliphatic Ketones: Synthesis of Enantioenriched Chiral Tertiary α‐Hydroxyboronates
Koji Kubota; Shun Osaki; Mingoo Jin; Hajime Ito
Angewandte Chemie, 129, 23, 6746, Wiley-Blackwell, Jun. 2017, [Peer-reviewed], [Corresponding author]
Scientific journal

Low-temperature-selective luminescent mechanochromism of a thienyl gold isocyanide complex
Tomohiro Seki; Koh Kobayashi; Hajime Ito
CHEMICAL COMMUNICATIONS, 53, 50, 6700, 6703, Jun. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Mechano-Responsive Luminescence via Crystal-to-Crystal Phase Transitions between Chiral and Non-Chiral Space Groups
Mingoo Jin; Tomohiro Seki; Hajime Ito
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 139, 22, 7452, 7455, Jun. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Luminescent Mechanochromic 9-Anthryl Gold(I) Isocyanide Complex with an Emission Maximum at 900 nm after Mechanical Stimulation
Tomohiro Seki; Noriaki Tokodai; Shun Omagari; Takayuki Nakanishi; Yasuchika Hasegawa; Takeshi Iwasa; Tetsuya Taketsugu; Hajime Ito
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 139, 19, 6514, 6517, May 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-Catalyzed Stereo- and Chemoselective Borylative Radical Cyclization of Alkyl Halides Bearing an Alkene Moiety
Hiroaki Iwamoto; Sota Akiyama; Keiichi Hayama; Hajime Ito
ORGANIC LETTERS, 19, 10, 2614, 2617, May 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Effective Photo- and Triboluminescent Europium(III) Coordination Polymers with Rigid Triangular Spacer Ligands
Yasuchika Hasegawa; Shiori Tateno; Masanori Yamamoto; Takayuki Nakanishi; Yuichi Kitagawa; Tomohiro Seki; Hajime Ito; Koji Fushimi
CHEMISTRY-A EUROPEAN JOURNAL, 23, 11, 2666, 2672, Feb. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Formal nucleophilic borylation and borylative cyclization of organic halides
K. Kubota; Iwamoto; H. Ito
ORGANIC & BIOMOLECULAR CHEMISTRY, 15, 2, 285, 300, Jan. 2017, [Peer-reviewed], [Corresponding author]
English

Copper(I)-Catalyzed Enantioselective Boryl Substitution of Allyl Acylals: An Efficient Approach for Enantioenriched -Chiral -Acetoxyallylboronates
Yuta Takenouchi; Ryoto Kojima; Riko Momma; Hajime Ito
SYNLETT, 28, 2, 270, 274, Jan. 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-Catalyzed Enantioselective Nucleophilic Borylation of Aliphatic Ketones: Synthesis of Enantioenriched Chiral Tertiary α-Hydroxyboronates
Koji Kubota; Shun Osaki; Mingoo Jin; Hajime Ito
Angewandte Chemie - International Edition, 56, 23, 6646, 6650, Wiley-VCH Verlag, 2017, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Transition-metal-free B-B and B-interelement reactions with organic molecules
Ana B. Cuenca; Ryosuke Shishido; Hajime Ito; Elena Fernandez
CHEMICAL SOCIETY REVIEWS, 46, 2, 415, 430, Jan. 2017, [Peer-reviewed], [Corresponding author]
English

Direct Introduction of a Dimesitylboryl Group Using Base-Mediated Substitution of Aryl Halides with Silyldimesitylborane
Eiji Yamamoto; Kiyotaka Izumi; Ryosuke Shishido; Tomohiro Seki; Noriaki Tokodai; Hajime Ito
CHEMISTRY-A EUROPEAN JOURNAL, 22, 49, 17547, 17551, Dec. 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Introduction of a Biphenyl Moiety for a Solvent-Responsive Aryl Gold(I) Isocyanide Complex with Mechanical Reactivation
Tomohiro Seki; Mingoo Jin; Hajime Ito
INORGANIC CHEMISTRY, 55, 23, 12309, 12320, Dec. 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Critical Role of Energy Transfer Between Terbium Ions for Suppression of Back Energy Transfer in Nonanuclear Terbium Clusters
Shun Omagari; Takayuki Nakanishi; Yuichi Kitagawa; Tomohiro Seki; Koji Fushimi; Hajime Ito; Andries Meijerink; Yasuchika Hasegawa
SCIENTIFIC REPORTS, 6, 37008, Nov. 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Luminescent Europium(III) Coordination Zippers Linked with Thiophene-Based Bridges
Yuichi Hirai; Takayuki Nakanishi; Yuichi Kitagawa; Koji Fushimi; Tomohiro Seki; Hajime Ito; Yasuchika Hasegawa
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 55, 39, 12059, 12062, Sep. 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Synthesis of Enantiomerically Enriched Chiral Tetrahydroquinolines via Sequential Dearomatization/Enantioselective Borylation Reactions
Koji Kubota; Yuta Watanabe; Hajime Ito
ADVANCED SYNTHESIS & CATALYSIS, 358, 15, 2379, 2384, Jul. 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Regioselective C-H Borylation of Heteroaromatic Aldimines with Iridium Complexes
Ikuo Sasaki; Toshiki Ikeda; Tatsunosuke Amou; Jumpei Taguchi; Hajime Ito; Tatsuo Ishiyama
SYNLETT, 27, 10, 1582, 1586, Jun. 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Computational Insight into the Enantioselective Nucleophilic Borylation of a Polarized C=O Double Bond Catalyzed by Diphosphine/Borylcopper(I) Complexes
Koji Kubota; Mingoo Jin; Hajime Ito
ORGANOMETALLICS, 35, 10, 1376, 1383, May 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Iridium(I)-catalyzed C-H Borylation of alpha,beta-Unsaturated Esters with Bis(pinacolato)diboron
Ikuo Sasaki; Jumpei Taguchi; Hana Doi; Hajime Ito; Tatsuo Ishiyama
CHEMISTRY-AN ASIAN JOURNAL, 11, 9, 1400, 1405, May 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

A Screening Approach for the Discovery of Mechanochromic Gold(I) Isocyanide Complexes with Crystal-to-Crystal Phase Transitions
Tomohiro Seki; Yuki Takamatsu; Hajime Ito
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 138, 19, 6252, 6260, May 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Enantioselective Synthesis of Chiral Piperidines via the Stepwise Dearomatization/Borylation of Pyridines
Koji Kubota; Yuta Watanabe; Keiichi Hayama; Hajime Ito
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 138, 13, 4338, 4341, Apr. 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Hyper-stable organo-Eu-III luminophore under high temperature for photo-industrial application
Ayako Nakajima; Takayuki Nakanishi; Yuichi Kitagawa; Tomohiro Seki; Hajime Ito; Koji Fushimi; Yasuchika Hasegawa
SCIENTIFIC REPORTS, 6, 24458, Apr. 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Molecular-Level Understanding of Structural Changes of Organic Crystals Induced by Macroscopic Mechanical Stimulation
Tomohiro Seki; Hajime Ito
CHEMISTRY-A EUROPEAN JOURNAL, 22, 13, 4322, 4329, Mar. 2016, [Peer-reviewed], [Corresponding author]
English

Detailed Investigation of the Structural, Thermal, and Electronic Properties of Gold Isocyanide Complexes with Mechano-Triggered Single-Crystal-to-Single-Crystal Phase Transitions
Tomohiro Seki; Kenta Sakurada; Mai Muromoto; Shu Seki; Hajime Ito
CHEMISTRY-A EUROPEAN JOURNAL, 22, 6, 1968, 1978, Feb. 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Mechanical Path to a Photogenerated Structure: Ball Milling-Induced Phase Transition of a Gold(I) Complex
K. Sakurada; T. Seki; H. Ito
CrystEngComm, 18, 38, 7217, 7220, 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Mechanochromic Luminescence Based on Crystal-to-Crystal Transformation Mediated by a Transient Amorphous State
Shiki Yagai; Tomohiro Seki; Hiroaki Aonuma; Kohsuke Kawaguchi; Takashi Karatsu; Takuma Okura; Aya Sakon; Hidehiro Uekusa; Hajime Ito
CHEMISTRY OF MATERIALS, 28, 1, 234, 241, Jan. 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-Catalyzed Diastereoselective Borylative Exo-Cyclization of Alkenyl Aryl Ketones
Eiji Yamamoto; Ryoto Kojima; Koji Kubota; Hajime Ito
SYNLETT, 27, 2, 272, 276, Jan. 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Highly selective Markovnikov hydroboration of alkyl-substituted terminal alkenes with a phosphine-copper(I) catalyst
Hiroaki Iwamoto; Koji Kubota; Hajime Ito
CHEMICAL COMMUNICATIONS, 52, 35, 5916, 5919, 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Luminescent mechanochromism of a chiral complex: distinct crystal structures and color changes of racemic and homochiral gold(I) isocyanide complexes with a binaphthyl moiety
Mingoo Jin; Tomohiro Seki; Hajime Ito
CHEMICAL COMMUNICATIONS, 52, 52, 8083, 8086, 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Seven-Coordinate Luminophores: Brilliant Luminescence of Lanthanide Complexes with C-3v Geometrical Structures
Kei Yanagisawa; Takayuki Nakanishi; Yuichi Kitagawa; Tomohiro Seki; Tomoko Akama; Masato Kobayashi; Tetsuya Taketsugu; Hajime Ito; Koji Fushimi; Yasuchika Hasegawa
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 28, 4769, 4774, Oct. 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Enantioselective Borylative Dearomatization of Indoles through Copper(I) Catalysis
Koji Kubota; Keiichi Hayama; Hiroaki Iwamoto; Hajime Ito
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 54, 30, 8809, 8813, Jul. 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Catalyst-Controlled Regiodivergent CH Borylation of Multifunctionalized Heteroarenes by Using Iridium Complexes
Ikuo Sasaki; Jumpei Taguchi; Shotaro Hiraki; Hajime Ito; Tatsuo Ishiyama
CHEMISTRY-A EUROPEAN JOURNAL, 21, 25, 9236, 9241, Jun. 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Can Lipid Tissues Including Epicardial Adipose Tissue (EAT), Visceral Adipose Tissue (VAT) and Coronary Plaque Be Moving in the Same Direction?
Sadako Motoyama; Hajime Ito; Yukio Ozaki
CIRCULATION JOURNAL, 79, 5, 969, 971, May 2015, [Peer-reviewed], [Corresponding author]
English

Luminescent Coordination Glass: Remarkable Morphological Strategy for Assembled Eu(III) Complexes
Yuichi Hirai; Takayuki Nakanishi; Yuichi Kitagawa; Koji Fushimi; Tomohiro Seki; Hajime Ito; Hiroyuki Fueno; Kazuyoshi Tanaka; Toshifumi Satoh; Yasuchika Hasegawa
INORGANIC CHEMISTRY, 54, 9, 4364, 4370, May 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Enhanced Electric Dipole Transition in Lanthanide Complex with Organometallic Ruthenocene Units
Yasuchika Hasegawa; Nao Sato; Yuichi Hirai; Takayuki Nakanishi; Yuichi Kitagawa; Atsushi Kobayashi; Masako Kato; Tomohiro Seki; Hajime Ito; Koji Fushimi
JOURNAL OF PHYSICAL CHEMISTRY A, 119, 20, 4825, 4833, May 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Reaction Mechanism of the Anomalous Formal Nucleophilic Borylation of Organic Halides with Silylborane: Combined Theoretical and Experimental Studies
Ryohei Uematsu; Eiji Yamamoto; Satoshi Maeda; Hajime Ito; Tetsuya Taketsugu
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 137, 12, 4090, 4099, Apr. 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Effective Photosensitized Energy Transfer of Nonanuclear Terbium Clusters Using Methyl Salicylate Derivatives
Shun Omagari; Takayuki Nakanishi; Tomohiro Seki; Yuichi Kitagawa; Yumie Takahata; Koji Fushimi; Hajime Ito; Yasuchika Hasegawa
JOURNAL OF PHYSICAL CHEMISTRY A, 119, 10, 1943, 1947, Mar. 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Silicon-Tethered Strategy for Copper(I)-Catalyzed Stereo- and Regioselective Alkylboration of Alkynes
Koji Kubota; Hiroaki Iwamoto; Eiji Yamamoto; Hajime Ito
ORGANIC LETTERS, 17, 3, 620, 623, Feb. 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-catalyzed carbon-halogen bond-selective boryl substitution of alkyl halides bearing terminal alkene moieties
Hiroaki Iwamoto; Koji Kubota; Eiji Yamamoto; Hajime Ito
CHEMICAL COMMUNICATIONS, 51, 47, 9655, 9658, 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Mismatched changes of the photoluminescence and crystalline structure of a mechanochromic gold(I) isocyanide complex
Tomohiro Seki; Kenta Sakurada; Hajime Ito
CHEMICAL COMMUNICATIONS, 51, 73, 13933, 13936, 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

A peptide ligase and the ribosome cooperate to synthesize the peptide pheganomycin
Motoyoshi Noike; Takashi Matsui; Koichi Ooya; Ikuo Sasaki; Shouta Ohtaki; Yoshimitsu Hamano; Chitose Maruyama; Jun Ishikawa; Yasuharu Satoh; Hajime Ito; Hiroyuki Morita; Tohru Dairi
NATURE CHEMICAL BIOLOGY, 11, 1, 71, +, Jan. 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Boryl substitution of functionalized aryl-, heteroaryl- and alkenyl halides with silylborane and an alkoxy base: expanded scope and mechanistic studies
Eiji Yamamoto; Satoshi Ukigai; Hajime Ito
CHEMICAL SCIENCE, 6, 5, 2943, 2951, 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-Catalyzed Enantioselective Nucleophilic Borylation of Aldehydes: An Efficient Route to Enantiomerically Enriched alpha-Alkoxyorganoboronate Esters
Koji Kubota; Eiji Yamamoto; Hajime Ito
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 137, 1, 420, 424, Jan. 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Interconvertible multiple photoluminescence color of a gold(I) isocyanide complex in the solid state: solvent-induced blue-shifted and mechano-responsive red-shifted photoluminescence
Tomohiro Seki; Taichi Ozaki; Takuma Okura; Kiyotaka Asakura; Aya Sakon; Hidehiro Uekusa; Hajime Ito
CHEMICAL SCIENCE, 6, 4, 2187, 2195, 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Photoinduced single-crystal-to-single-crystal phase transition and photosalient effect of a gold(I) isocyanide complex with shortening of intermolecular aurophilic bonds
Tomohiro Seki; Kenta Sakurada; Mai Muromoto; Hajime Ito
CHEMICAL SCIENCE, 6, 2, 1491, 1497, 2015, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-Catalyzed Enantioselective Synthesis of alpha-Chiral Linear or Carbocyclic (E)-(gamma-Alkoxyallyl)boronates
Eiji Yamamoto; Yuta Takenouchi; Taichi Ozaki; Takanori Miya; Hajime Ito
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136, 47, 16515, 16521, Nov. 2014, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Enhancement of Optical Faraday Effect of Nonanuclear Tb(III) Complexes
Takayuki Nakanishi; Yuki Suzuki; Yoshihiro Doi; Tomohiro Seki; Hitoshi Koizumi; Koji Fushimi; Koji Fujita; Yukio Hinatsu; Hajime Ito; Katsuhisa Tanaka; Yasuchika Hasegawa
INORGANIC CHEMISTRY, 53, 14, 7635, 7641, Jul. 2014, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Selective Synthesis of Organoboron Compounds with Copper(I)-PhosPhine Complex Catalysts
Eiji Yamamoto; Yuta Takenouchi; Koji Kubota; Hajime Ito
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 72, 7, 758, 769, Jul. 2014, [Peer-reviewed], [Corresponding author]
Japanese

Design amphiphilic dipolar pi-systems for stimuli-responsive luminescent materials using metastable states
Shiki Yagai; Satoru Okamura; Yujiro Nakano; Mitsuaki Yamauchi; Keiki Kishikawa; Takashi Karatsu; Akihide Kitamura; Akira Ueno; Daiki Kuzuhara; Hiroko Yamada; Tomohiro Seki; Hajime Ito
NATURE COMMUNICATIONS, 5, Jun. 2014, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Formal Nucleophilic Boryl Substitution of Organic Halides with Silylborane/Alkoxy Base System
Eiji Yamamoto; Kiyotaka Izumi; Yuko Horita; Satoshi Ukigai; Hajime Ito
TOPICS IN CATALYSIS, 57, 10-13, 940, 945, Jun. 2014, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Carbon-Boron and Carbon-Silicon Bond Formation
Masaya Sawamura; Hajime Ito
Copper-Catalyzed Asymmetric Synthesis, 157, 178, Wiley Blackwell, 31 Mar. 2014, [Peer-reviewed], [Corresponding author]
English, In book

Back Cover: Cationic Ir/Me-BIPAM-Catalyzed Asymmetric Intramolecular Direct Hydroarylation of α-Ketoamides (Angew. Chem. Int. Ed. 10/2014)
Tomohiko Shirai; Hajime Ito; Yasunori Yamamoto
Angewandte Chemie International Edition, 53, 10, 2778, 2778, Wiley, 03 Mar. 2014, [Peer-reviewed], [Corresponding author]
Scientific journal

Cationic Ir/Me-BIPAM-Catalyzed Asymmetric Intramolecular Direct Hydroarylation of alpha-Ketoamides
Tomohiko Shirai; Hajime Ito; Yasunori Yamamoto
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 53, 10, 2658, 2661, Mar. 2014, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Iridium-catalyzed ortho-C-H borylation of aromatic aldimines derived from pentafluoroaniline with bis(pinacolate)diboron
Ikuo Sasaki; Tatsunosuke Amou; Hajime Ito; Tatsuo Ishiyama
ORGANIC & BIOMOLECULAR CHEMISTRY, 12, 13, 2041, 2044, 2014, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Aromatic C-H silylation of arenes with 1-hydrosilatrane catalyzed by an iridium(I)/2,9-dimethylphenanthroline (dmphen) complex
Tatsuo Ishiyama; Takeaki Saiki; Emi Kishida; Ikuo Sasaki; Hajime Ito; Norio Miyaura
ORGANIC & BIOMOLECULAR CHEMISTRY, 11, 47, 8162, 8165, Dec. 2013, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Controlling Mechano- and Seeding-Triggered Single-Crystal-to-Single-Crystal Phase Transition: Molecular Domino with a Disconnection of Aurophilic Bonds
Tomohiro Seki; Kenta Sakurada; Hajime Ito
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 52, 49, 12828, 12832, Dec. 2013, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Effect of Ligand Polarization on Asymmetric Structural Formation for Strongly Luminescent Lanthanide Complexes
Yasuchika Hasegawa; Tomoki Ohkubo; Takayuki Nakanishi; Atsushi Kobayashi; Masako Kato; Tomohiro Seki; Hajime Ito; Koji Fushimi
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2013, 34, 5911, 5918, Dec. 2013, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Regio- and Enantioselective Monoborylation of Alkenylsilanes Catalyzed by an Electron-Donating Chiral Phosphine-Copper(I) Complex
Koji Kubota; Eiji Yamamoto; Hajime Ito
ADVANCED SYNTHESIS & CATALYSIS, 355, 18, 3527, 3531, Dec. 2013, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Luminescence Color-Tuning through Polymorph Doping: Preparation of a White-Emitting Solid from a Single Gold(I)-Isocyanide Complex by Simple Precipitation
Tomohiro Seki; Sayaka Kurenuma; Hajime Ito
CHEMISTRY-A EUROPEAN JOURNAL, 19, 48, 16214, 16220, Nov. 2013, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Tetrabutylammonium 2-Pyridyltriolborate Salts for Suzuki-Miyaura Cross-Coupling Reactions with Aryl Chlorides
Shohei Sakashita; Miho Takizawa; Juugaku Sugai; Hajime Ito; Yasunori Yamamoto
ORGANIC LETTERS, 15, 17, 4308, 4311, Sep. 2013, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Mechanical stimulation and solid seeding trigger single-crystal-to-single-crystal molecular domino transformations
Hajime Ito; Mai Muromoto; Sayaka Kurenuma; Shoji Ishizaka; Noboru Kitamura; Hiroyasu Sato; Tomohiro Seki
NATURE COMMUNICATIONS, 4, Jun. 2013, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-catalyzed borylative exo -cyclization of alkenyl halides containing unactivated double bond
Koji Kubota; Eiji Yamamoto; Hajime Ito
Journal of the American Chemical Society, 135, 7, 2635, 2640, 20 Feb. 2013, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Cross-Coupling Reaction with Lithium Methyltriolborate
Yasunori Yamamoto; Kazuya Ikizakura; Hajime Ito; Norio Miyaura
MOLECULES, 18, 1, 430, 439, Jan. 2013, [Peer-reviewed], [Invited], [Corresponding author]
English, Scientific journal

Iridium(I)-catalyzed vinylic C-H borylation of 1-cycloalkenecarboxylates with bis(pinacolato)diboron
Ikuo Sasaki; Hana Doi; Toshiya Hashimoto; Takao Kikuchi; Hajime Ito; Tatsuo Ishiyama
CHEMICAL COMMUNICATIONS, 49, 68, 7546, 7548, 2013, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Cholesterol-aided construction of distinct self-organized materials from a luminescent gold(I)-isocyanide complex exhibiting mechanochromic luminescence
Kohsuke Kawaguchi; Tomohiro Seki; Takashi Karatsu; Akihide Kitamura; Hajime Ito; Shiki Yagai
CHEMICAL COMMUNICATIONS, 49, 97, 11391, 11393, 2013, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Luminescent Mechanochromism and Spontaneous Phase Transformation of Gold(I) Isocyanide Complexes
Ito Hajime; Seki Tomohir
Bulletin of Japan Society of Coordination Chemistry, 62, 3, 11, Japan Society of Coordination Chemistry, 2013, [Peer-reviewed], [Corresponding author]
English, Aryl gold isocyanide complexes are found to have interesting photoluminescence properties in the solid state, being referred to as luminescence mechanochromism and molecular domino. A gold complex containing two gold atoms, {[pentafluorophenylgold]₂(μ-1,4-diisocyanobenzene)}, shows significant change in its luminescence property when mechanical stimulus such as grinding or pressing is applied on its solid sample. This "luminescence mechanochromism" is most probably attributed to a ground state structure change from the microcrystalline to the amorphous state accompanied to the optical properties alternations. Different feature observed in phenyl(phenyl isocyanide)gold(I) complex is "molecular domino", where even a small mechanical stimulus can trigger the structure change of the entire crystal. This spontaneous structure change proceeded in a single-crystal-to-single-crystal fashion with the drastic emission color alternation. These features enable sub-molecular-level structure investigation with single X-ray crystallographic analysis and visual observation of the phase transition under UV light irradiation during the mechano-induced phase change.

Anomalous Reactivity of Silylborane: Transition-Metal-Free Boryl Substitution of Aryl, Alkenyl, and Alkyl Halides with Silylborane/Alkoxy Base Systems
Eiji Yamamoto; Kiyotaka Izumi; Yuko Horita; Hajime Ito
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 134, 49, 19997, 20000, Dec. 2012, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Me-BIPAM for the Synthesis of Optically Active 3-Aryl-3-hydroxy-2-oxindoles by Ruthenium-catalyzed Addition of Arylboronic Acids to Isatins
Yasunori Yamamoto; Masaaki Yohda; Tomohiko Shirai; Hajime Ito; Norio Miyaura
CHEMISTRY-AN ASIAN JOURNAL, 7, 10, 2446, 2449, Oct. 2012, [Peer-reviewed], [Corresponding author]
English, Scientific journal

ASYMMETRIC CATALYSIS The power of pairing
Hajime Ito
NATURE CHEMISTRY, 4, 6, 438, 439, Jun. 2012, [Peer-reviewed], [Corresponding author]
English

Practical procedure for copper(I)-catalyzed allylic boryl substitution with stoichiometric alkoxide base
Hajime Ito; Takanori Miya; Masaya Sawamura
TETRAHEDRON, 68, 17, 3423, 3427, Apr. 2012, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-Catalyzed Allylic Substitution of Silyl Nucleophiles through Si?Si Bond Activation
Hajime Ito; Yuko Horita; Masaya Sawamura
ADVANCED SYNTHESIS & CATALYSIS, 354, 5, 813, 817, Mar. 2012, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-Catalyzed Boryl Substitution of Unactivated Alkyl Halides
Hajime Ito; Koji Kubota
ORGANIC LETTERS, 14, 3, 890, 893, Feb. 2012, [Peer-reviewed], [Corresponding author]
English, Scientific journal

A rapid and sensitive LC/ESI-MS/MS method for quantitative analysis of docetaxel in human plasma and its application to a pharmacokinetic study
Yamaguchi, H.; Fujikawa, A.; Ito, H.; Tanaka, N.; Furugen, A.; Miyamori, K.; Takahashi, N.; Ogura, J.; Kobayashi, M.; Yamada, T.; Mano, N.; Iseki, K.
Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences, 893-894, 2012, [Peer-reviewed], [Corresponding author]
Scientific journal

Potassium tert-butoxide-mediated regioselective silaboration of aromatic alkenes
Hajime Ito; Yuko Horita; Eiji Yamamoto
CHEMICAL COMMUNICATIONS, 48, 64, 8006, 8008, 2012, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Mechanistic Insight into the Anomalous syn-Selectivity Observed during the Addition of Allenylboronates to Aromatic Aldehydes
Yusuke Sasaki; Masaya Sawamura; Hajime Ito
CHEMISTRY LETTERS, 40, 9, 1044, 1046, Sep. 2011, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-Catalyzed Regioselective Monoborylation of 1,3-Enynes with an Internal Triple Bond: Selective Synthesis of 1,3-Dienylboronates and 3-Alkynylboronates
Yusuke Sasaki; Yuko Horita; Chongmin Zhong; Masaya Sawamura; Hajime Ito
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 50, 12, 2778, 2782, 2011, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Direct enantio-convergent transformation of racemic substrates without racemization or symmetrization
Hajime Ito; Shun Kunii; Masaya Sawamura
NATURE CHEMISTRY, 2, 11, 972, 976, Nov. 2010, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Enantioselective Synthesis of trans-Aryl- and -Heteroaryl-Substituted Cyclopropylboronates by Copper(I)-Catalyzed Reactions of Allylic Phosphates with a Diboron Derivative
Chongmin Zhong; Shun Kunii; Yuki Kosaka; Masaya Sawamura; Hajime Ito
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 132, 33, 11440, 11442, Aug. 2010, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Stereospecific Synthesis of Cyclobutylboronates through Copper(I)-Catalyzed Reaction of Homoallylic Sulfonates and a Diboron Derivative
Hajime Ito; Takashi Toyoda; Masaya Sawamura
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 132, 17, 5990, +, May 2010, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper(I)-Catalyzed Asymmetric Monoborylation of 1,3-Dienes: Synthesis of Enantioenriched Cyclic Homoallyl- and Allylboronates
Yusuke Sasaki; Chongmin Zhong; Masaya Sawamura; Hajime Ito
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 132, 4, 1226, +, Feb. 2010, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Desymmetrization of meso-2-Alkene-1,4-diol Derivatives through Copper(I)-Catalyzed Asymmetric Boryl Substitution and Stereoselective Allylation of Aldehydes
Hajime Ito; Takuma Okura; Kou Matsuura; Masaya Sawamura
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 49, 3, 560, 563, 2010, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Gold(I) Hydride Intermediate in Catalysis: Dehydrogenative Alcohol Silylation Catalyzed by Gold(I) Complex
Hajime Ito; Tomohisa Saito; Takahiro Miyahara; Chongmin Zhong; Masaya Sawamura
ORGANOMETALLICS, 28, 16, 4829, 4840, Aug. 2009, [Peer-reviewed], [Corresponding author]
English

The synthesis of allenes by Cu(I)-catalyzed regio- and stereoselective reduction of propargylic carbonates with hydrosilanes
Chongmin Zhong; Yusuke Sasaki; Hajime Ito; Masaya Sawamura
CHEMICAL COMMUNICATIONS, 39, 5850, 5852, 2009, [Peer-reviewed], [Corresponding author]
English, Scientific journal

New Synthetic Reactions through sigma-Bond Metathesis of Group 11 Metal Catalysts
Hajime Ito
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 66, 12, 1168, 1177, Dec. 2008, [Peer-reviewed], [Corresponding author]
Japanese, Scientific journal

Copper(I)-Catalyzed Substitution of Propargylic Carbonates with Diboron: Selective Synthesis of Multisubstituted Allenylboronates
Hajime Ito; Yusuke Sasaki; Masaya Sawamura
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 130, 47, 15774, +, Nov. 2008, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Enantioselective Addition of Terminal Alkynes to Aromatic Aldehydes Catalyzed by Copper(I) Complexes with Wide-Bite-Angle Chiral Bisphosphine Ligands: Optimization, Scope, and Mechanistic Studies
Yohsuke Asano; Hajime Ito; Kenji Hara; Masaya Sawamura
ORGANOMETALLICS, 27, 22, 5984, 5996, Nov. 2008, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Reversible mechanochromic luminescence of
Hajime Ito; Tomohisa Saito; Naoya Oshima; Noboru Kitamura; Shoji Ishizaka; Yukio Hinatsu; Makoto Wakeshima; Masako Kato; Kiyoshi Tsuge; Masaya Sawamura
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 130, 31, 10044, +, Aug. 2008, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper-catalyzed substitution of allylic carbonates with diboron: A new approach to allylboronate synthesis
Hajime Ito; Shinichiro Ito; Yusuke Sasaki; Kou Matsuura; Masaya Sawamura
PURE AND APPLIED CHEMISTRY, 80, 5, 1039, 1045, May 2008, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Synthesis of optically active boron-silicon bifunctional cyclopropane derivatives through enantioselective copper(I)-catalyzed reaction of allylic carbonates with a diboron derivative
Hajime Ito; Yuki Kosaka; Kousuke Nonoyama; Yusuke Sasaki; Masaya Sawamura
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 47, 39, 7424, 7427, 2008, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper-catalyzed enantioselective substitution of allylic carbonates with diboron: An efficient route to optically active alpha-chiral allylboronates
Hajime Ito; Shinichiro Ito; Yusuke Sasaki; Kou Matsuura; Masaya Sawamura
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 129, 48, 14856, +, Dec. 2007, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Synthesis and structural characterization of a tetranuclear platinum(II) metallamacrocycle containing 1,3-diisocyanoarene ligands
Hajime Ito; Tsuyoshi Maeda; Masaya Sawamura
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 80, 10, 1981, 1986, Oct. 2007, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Enantioselective addition of terminal alkynes to aldehydes catalyzed by a Cu(I)-TRAP complex
Yohsuke Asano; Kenji Hara; Hajime Ito; Masaya Sawamura
ORGANIC LETTERS, 9, 20, 3901, 3904, Sep. 2007, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Design and synthesis of isocyanide Ligands for catalysis: Application to rh-catalyzed hydrosilylation of ketones
Hajime Ito; Takayuki Kato; Masaya Sawamura
CHEMISTRY-AN ASIAN JOURNAL, 2, 11, 1436, 1446, 2007, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Synthesis of new bulky isocyanide ligands and their use for Rh-catalyzed hydrosilylation
Hajime Ito; Takayuki Kato; Masaya Sawamura
CHEMISTRY LETTERS, 35, 9, 1038, 1039, Sep. 2006, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Electronically tunable compact trialkylphosphines: SMAPs-bridged bicyclic phosphines
A Ochida; S Ito; T Miyahara; H Ito; M Sawamura
CHEMISTRY LETTERS, 35, 3, 294, 295, Mar. 2006, [Peer-reviewed], [Corresponding author]
English, Scientific journal

A novel strategy for fluorescence enhancement in the soild-state: affording rigidity to fuluorophores packing
Y. Mizobe; N. Tohnai; H. Ito; M. Miyata; Y. Hasegawa
Chem. Commun., 20, 2126, 2128, 2006, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Copper-catalyzed gamma-selective and stereospecific substitution reaction of allylic carbonates with diboron: Efficient route to chiral allylboron compounds
H Ito; C Kawakami; M Sawamura
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 127, 46, 16034, 16035, Nov. 2005, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Gold(I)-phosphine catalyst for the highly chemoselective dehydrogenative silylation of alcohols
H Ito; K Takagi; T Miyahara; M Sawamura
ORGANIC LETTERS, 7, 14, 3001, 3004, Jul. 2005, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Versatile dehydrogenative alcohol silylation catalyzed by Cu(I)-phosphine complex
H Ito; A Watanabe; M Sawamura
ORGANIC LETTERS, 7, 9, 1869, 1871, Apr. 2005, [Peer-reviewed], [Lead author, Corresponding author]
English, Scientific journal

Nonvolatile Me3P-like P-donor ligand: Synthesis and properties of 4-phenyl-1-phospha-4-silabicyclo[2.2.2]octane
A Ochida; K Hara; H Ito; M Sawamura
ORGANIC LETTERS, 5, 15, 2671, 2674, Jul. 2003, [Peer-reviewed], [Corresponding author]
English, Scientific journal

New reactivity of a reducing reagent generated from a copper(I) salt and a hydrosilane: Selective reduction of ketones and olefins conjugated with an aromatic group
H Ito; H Yamanaka; T Ishizuka; J Tateiwa; A Hosomi
SYNLETT, 4, 479, 482, Apr. 2000, [Peer-reviewed], [Lead author]
English, Scientific journal

New synthetic reactions using group 11 metal compounds as a catalyst
H Ito; A Hosomi
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 58, 4, 274, 284, Apr. 2000, [Peer-reviewed], [Corresponding author]
Japanese, Scientific journal

First gold complex-catalysed selective hydrosilylation of organic compounds
H Ito; T Yajima; J Tateiwa; A Hosomi
CHEMICAL COMMUNICATIONS, 11, 981, 982, 2000, [Peer-reviewed], [Lead author]
English, Scientific journal

An unprecedented catalytic reaction using gold(I) complexes
H Ito; T Yajima; J Tateiwa; A Hosomi
TETRAHEDRON LETTERS, 40, 44, 7807, 7810, Oct. 1999, [Peer-reviewed], [Lead author]
English, Scientific journal

Highly stereoselective metathesis reaction between optically active hydrosilane and copper(I) salt in 1,3-dimethyl-2-imidazolidinone
H Ito; T Ishizuka; T Okumura; H Yamanaka; J Tateiwa; M Sonoda; A Hosomi
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 574, 1, 102, 106, Feb. 1999, [Peer-reviewed], [Lead author]
English, Scientific journal

Intramolecular hydrogen bond-promoted C-C bond formation: reaction rate enhancement and regioselective allylation of carbonyl compounds
H Ito; Y Ujita; J Tateiwa; M Sonoda; A Hosomi
CHEMICAL COMMUNICATIONS, 22, 2443, 2444, Nov. 1998, [Peer-reviewed], [Lead author]
English, Scientific journal

Studies on organosilicon chemistry. Part 145. New method for introduction of a silyl group into alpha,beta-enones using a disilane catalyzed by a copper(I) salt
H Ito; T Ishizuka; J Tateiwa; M Sonoda; A Hosomi
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 120, 43, 11196, 11197, Nov. 1998, [Peer-reviewed], [Lead author]
English, Scientific journal

Selective O-acylation of silyl enol ethers with acid halides mediated by a copper(I) salt
H Ito; T Ishizuka; J Tateiwa; A Hosomi
TETRAHEDRON LETTERS, 39, 35, 6295, 6298, Aug. 1998, [Peer-reviewed], [Lead author]
English, Scientific journal

Uncatalyzed aldol reaction using a dimethylsilyl enolate and alpha-dimethylsilyl ester in N,N-dimethylformamide
K Miura; H Sato; K Tamaki; H Ito; A Hosomi
TETRAHEDRON LETTERS, 39, 17, 2585, 2588, Apr. 1998, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Di-functionalization of alkenes using an oxidant generated from manganese(II) chloride under oxygen: Synthesis of gamma-lactones
M Hojo; C Murakami; K Ohno; J Kuboyama; S Nakamura; H Ito; A Hosomi
HETEROCYCLES, 47, 1, 97, 100, Jan. 1998, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Palladium-catalyzed coupling reactions of N-methoxy-N-methylcarbamoyl chloride for the synthesis of N-methoxy-N-methylamides
M Murakami; Y Hoshino; H Ito; Y Ito
CHEMISTRY LETTERS, 2, 163, 164, 1998, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Studies on organosilicon chemistry. 138. Generation of a reducing reagent from copper(I) salt and hydrosilane. New practical method for conjugate reduction
H Ito; T Ishizuka; K Arimoto; K Miura; A Hosomi
TETRAHEDRON LETTERS, 38, 51, 8887, 8890, Dec. 1997, [Peer-reviewed], [Lead author]
English, Scientific journal

A new type of allyl- and prop-2-ynyl-manganese species: generation and reactions with electrophiles
M Hojo; H Harada; H Ito; A Hosomi
CHEMICAL COMMUNICATIONS, 21, 2077, 2078, Nov. 1997, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Highly stereoselective intramolecular addition of a hydroxyl group to vinylsilanes via 1,2-silyl migration
K Miura; T Hondo; H Saito; H Ito; A Hosomi
JOURNAL OF ORGANIC CHEMISTRY, 62, 24, 8292, 8293, Nov. 1997, [Peer-reviewed], [Corresponding author]
English

Direct alkynyl group transfer from silicon to copper: New preparation method of alkynylcopper (I) reagents
H Ito; K Arimoto; H Sensui; A Hosomi
TETRAHEDRON LETTERS, 38, 22, 3977, 3980, Jun. 1997, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Manganese ate complexes as new reducing agents: Perfectly regiocontrolled generation and reactions of the manganese enolates with electrophiles
M Hojo; H Harada; H Ito; A Hosomi
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 119, 23, 5459, 5460, Jun. 1997, [Peer-reviewed], [Corresponding author]
English, Scientific journal

New access to cross-coupling reaction between arylsilanes or heteroarylsilanes and aryl halides mediated by a copper(I) salt
H Ito; H Sensui; K Arimoto; K Miura; A Hosomi
CHEMISTRY LETTERS, 7, 639, 640, 1997, [Peer-reviewed], [Lead author]
English, Scientific journal

''Tailor-made'' carbonyl ylides: [3+2]cycloaddition of the parent and optionally substituted nonstabilized carbonyl ylides
M Hojo; H Aihara; H Ito; A Hosomi
TETRAHEDRON LETTERS, 37, 51, 9241, 9244, Dec. 1996, [Peer-reviewed]
English, Scientific journal

Titanocene- and zirconocene-mediated cyclization of allyl propargyl ethers. Stereoselective synthesis of 3-methylenetetrahydrofurans
K Miura; M Funatsu; H Saito; H Ito; A Hosomi
TETRAHEDRON LETTERS, 37, 50, 9059, 9062, Dec. 1996, [Peer-reviewed]
English, Scientific journal

Allylstannylation of alkynes via a radical process: Stereoselective synthesis of di- and tri-substituted vinylstannanes
K Miura; D Itoh; T Hondo; H Saito; H Ito; A Hosomi
TETRAHEDRON LETTERS, 37, 47, 8539, 8542, Nov. 1996, [Peer-reviewed]
English, Scientific journal

Allylstannylation of alkenes via radical process
K Miura; T Matsuda; T Hondo; H Ito; A Hosomi
SYNLETT, 1996, 6, 555, &, Jun. 1996, [Peer-reviewed]
English, Scientific journal

Alkyllithium-mediated anomalous trimerization of 2,6-xylyl isocyanide
M Murakami; H Ito; Y Ito
CHEMISTRY LETTERS, 1, 7, 8, 1996, [Peer-reviewed]
English, Scientific journal

Preparation of (alkaneimidoyl)lanthanides and their reactions with carbonyl compounds
M Murakami; H Ito; Y Ito
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 69, 1, 25, 30, Jan. 1996, [Peer-reviewed]
English, Scientific journal

Regio- and stereoselective incorporation of a C-13 nuclide into D-ribo-phytosphingosine via SmI2-mediated C-C formation with C-13-labeled isocyanide
M Murakami; H Ito; Y Ito
CHEMISTRY LETTERS, 3, 185, 186, 1996, [Peer-reviewed]
English, Scientific journal

STEREOSELECTIVE SYNTHESIS OF 2-AMINO ALCOHOLS BY USE OF AN ISOCYANIDE AS AN AMINOMETHYLENE EQUIVALENT
M MURAKAMI; H ITO; Y ITO
JOURNAL OF ORGANIC CHEMISTRY, 58, 24, 6766, 6770, Nov. 1993, [Peer-reviewed]
English, Scientific journal

SYNTHESIS OF ALPHA-HYDROXY KETONES BY SAMARIUM(II) IODIDE-MEDIATED COUPLING OF ORGANIC HALIDES, AN ISOCYANIDE, AND CARBONYL-COMPOUNDS
M MURAKAMI; T KAWANO; H ITO; Y ITO
JOURNAL OF ORGANIC CHEMISTRY, 58, 6, 1458, 1465, Mar. 1993, [Peer-reviewed], [Corresponding author]
English, Scientific journal

THE PREPARATION OF [1-(ARYLIMINO)ALKYL]ZINC BY THE ALPHA-ADDITION OF ORGANOZINC TO ISOCYANIDE
M MURAKAMI; H ITO; Y ITO
JOURNAL OF ORGANIC CHEMISTRY, 53, 17, 4158, 4159, Aug. 1988, [Peer-reviewed], [Corresponding author]
English

Development of Selective Reactions Using Ball Milling
Koji Kubota; Hajime Ito, JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 79, 5, 492, 502, May 2021
Japanese, Book review

Mechanochemical Cross-Coupling Reactions
Koji Kubota; Hajime Ito, TRENDS IN CHEMISTRY, 2, 12, 1066, 1081, Dec. 2020
English, Book review

Development of mechanoredox reactions using ball milling and piezoelectric materials
久保田浩司; 久保田浩司; PANG Yadong; 三浦章; 伊藤肇; 伊藤肇, 日本化学会春季年会講演予稿集(CD-ROM), 100th, 2020

Olefin-accelerated C-N cross-coupling in the solid-state
Koji Kubota; Tamae Seo; Katsumasa Koide; Yasuchika Hasegawa; Hajime Ito, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 258, Aug. 2019
English, Summary international conference

Mechanochemical iridium-catalyzed C-H borylation
Yadong Pang; Tatsuo Ishiyama; Koji Kubota; Hajime Ito, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 258, Aug. 2019
English, Summary international conference

Olefin-accelerated C-C cross-coupling reaction in solid-state
Tamae Seo; Tatsuo Ishiyama; Koji Kubota; Hajime Ito, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 258, Aug. 2019
English, Summary international conference

Soft crystal force field for elucidation of crystal-crystal phase transition of gold isocyanide complexes
Naofumi Nakayama; Shigeaki Obata; Hitoshi Gotoh; Tomohiro Seki; Hajime Ito, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 255, Mar. 2018
English, Summary international conference

ソフトクリスタルの多形転移解析法の探求
堀芳和; 榎本大義; 小畑繁昭; 中山尚史; 後藤仁志; 関朋宏; 伊藤肇, 日本コンピュータ化学会年会講演予稿集, 2018, 41, 2018
Japanese

Control of Luminescent Properties and Long Wavelength Emission of Mechanochromic Compounds
関 朋宏; 伊藤 肇, 光化学 = Photochemistry : 光化学協会会誌, 48, 2, 81, 84, Aug. 2017
光化学協会, Japanese

Copper(I)-Catalyzed Borylative exo-Cyclization of Alkenyl Halides Containing Unactivated Double Bond (vol 135, pg 2635, 2013)
Koji Kubota; Eiji Yamamoto; Hajime Ito, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 137, 39, 12729, 12729, Oct. 2015
English, Others

金原子間相互作用の増強に誘起された金イソシアニド錯体の光相転移とPhotosalient効果
関朋宏; 伊藤肇, 光化学討論会講演要旨集, 2015, CD-ROM, ROMBUNNO.3C07, 08 Sep. 2015
Japanese

研究室紹介
伊藤 肇; 石山 竜生; 関 朋宏, Organometallic News, 2015, 3, 112, 113, 06 Aug. 2015
近畿化学協会, Japanese

研究室紹介
伊藤 肇; 石山 竜生; 関 朋宏, Organometallic News, 2015, 3, 112, 113, 06 Aug. 2015
近畿化学協会, Japanese

七配位構造を有する希土錯体の光物性評価
柳澤慧; 中西貴之; 北川裕一; 関朋宏; 伏見公志; 伊藤肇; 長谷川靖哉, 希土類, 66, 82, 83, 14 May 2015
Japanese

光と魔法の高分子 発光色がショックで変化する分子ドミノ
関朋宏; 伊藤肇, 高分子, 64, 4, 205, 206, 01 Apr. 2015
Japanese

機械的刺激や溶媒添加により三つの発光色が切り替わるビアリール金(I)イソシアニド錯体
JIN Mingoo; 関朋宏; 伊藤肇, 日本化学会講演予稿集, 95th, 3, 642, 11 Mar. 2015
Japanese

赤外発光を示すアントラセン金(I)イソシアニド錯体の光学特性と結晶構造
戸子台遥光; 関朋宏; 大曲駿; 中西貴之; 長谷川靖哉; 伊藤肇, 日本化学会講演予稿集, 95th, 3, 643, 11 Mar. 2015
Japanese

金イソシアニド錯体のマルチカラーメカノクロミズム
関朋宏; 尾崎太一; 大倉拓真; 佐近彩; 植草秀裕; 伊藤肇, 日本化学会講演予稿集, 95th, 3, 671, 11 Mar. 2015
Japanese

Photoinduced Crystalline Structure Change and Photosalient Effect through Strengthening Metallophilic Interaction
関朋宏; 伊藤肇, 日本結晶学会誌, 57, 4, 226-232 (J-STAGE), 232, 2015
We report the first photoinduced single-crystal-to-single-crystal (SCSC) phase transition of a gold complex <b>1</b> that involves strengthening of intermolecular aurophilic interactions. This is also the first solid state photochromism of gold complexes. Upon UV irradiation, blue-emitting crystals <b>1B</b> of aryl gold(I) isocyanide complex <b>1</b> transform into the weakly yellow-emitting crystals <b>1Y</b>. X-ray diffraction analyses exhibit that the phase transition proceeds in an SCSC manner. After phase transition from <b>1B</b> to <b>1Y</b>, the intermolecular Au…Au separation decreases from 3.5041(14) to 3.2955(6) Å, resulting in a red-shifted emission. The photoinduced strengthening of the aurophilic interactions in the excited state initiates the change in the crystal structure from <b>1B</b> to <b>1Y</b>. Moreover, crystal <b>1B</b> showed a photosalient effect: the <b>1B</b> crystals jump upon irradiation with strong UV light owing to the phase transition into <b>1Y</b>. The photoinduced strengthening of aurophilic interactions in the crystal generate the sudden mechanical movement of the crystal., The Crystallographic Society of Japan, Japanese

Molecular domino with emission color change upon applying mechanical stimulus
Tomohiro Seki; Hajime Ito, Kobunshi, 64, 205, 206, 01 Jan. 2015

光照射による金原子間相互作用の増強に誘起された金イソシアニド錯体の単結晶‐単結晶相転移
関朋宏; 櫻田健太; 伊藤肇, 高分子学会予稿集(CD-ROM), 63, 2, ROMBUNNO.2U13, 03 Sep. 2014
Japanese

私の自慢 銅(Ⅰ)錯体触媒による合成反応開発と発光性金(Ⅰ)錯体の 動的挙動 : 偶然の発見が自分の研究の幅を広げてくれました!
伊藤 肇, 化学と工業 = Chemistry & chemical industry, 67, 9, 793, 795, Sep. 2014
日本化学会, Japanese

位置異性配位子を有する発光性Eu(III)錯体の形態制御
平井悠一; 中西貴之; 関朋宏; 伊藤肇; 佐藤敏文; 伏見公志; 長谷川靖哉, 錯体化学会討論会講演要旨集, 64th, 20, 01 Sep. 2014
Japanese

金属錯体で架橋したEu(III)配位高分子の合成と光物性
山本昌紀; 中西貴之; 関朋宏; 伊藤肇; 伏見公志; 長谷川靖哉, 配位化合物の光化学討論会講演要旨集, 26th, 134, 135, 06 Aug. 2014
Japanese

金原子間距離短縮を伴う金イソシアニド錯体の光をトリガーとした単結晶‐単結晶相転移
櫻田健太; 関朋宏; 伊藤肇, 万有生命科学振興国際交流財団仙台シンポジウム, 25th, 52, 14 Jun. 2014
Japanese

金(I)イソシアニド錯体の発光特性及びメカノクロミズム特性に対する置換基効果
高松雄輝; 関朋宏; 伊藤肇, 日本化学会講演予稿集, 94th, 2, 377, 12 Mar. 2014
Japanese

キラル配位子を導入した九核Tb(III)クラスターの合成と光物性
和田智志; 中西貴之; 関朋宏; 伊藤肇; 小西克明; 伏見公志; 長谷川靖哉, 日本化学会講演予稿集, 94th, 2, 422, 12 Mar. 2014
Japanese

金原子間相互作用の形成を伴う金イソシアニド錯体の光に誘起される単結晶‐単結晶相転移
櫻田健太; 室本麻衣; 関朋宏; 伊藤肇, 日本化学会講演予稿集, 94th, 2, 377, 12 Mar. 2014
Japanese

平面四配位型Pd(II)錯体で架橋されたEu(III)配位高分子の合成と光物性
山本昌紀; 中西貴之; 関朋宏; 伊藤肇; 伏見公志; 長谷川靖哉, 日本化学会講演予稿集, 94th, 2, 420, 12 Mar. 2014
Japanese

Development of Novel Copper-Catalyzed Synthesis of Organoboron Compounds and Luminescence Gold Complexes with Mechanical Response Properties
伊藤 肇, 化学と工業, 67, 3, 201, 201, 01 Mar. 2014
日本化学会, Japanese

九核Tb(III)クラスターの合成と光磁気特性
鈴木勇喜; 土井貴弘; 日夏幸雄; 関朋宏; 伊藤肇; 小泉均; 中西貴之; 伏見公志; 長谷川靖哉, 化学系学協会北海道支部冬季研究発表会講演要旨集(CD-ROM), 2014, ROMBUNNO.1A09, 28 Jan. 2014
Japanese

自己集積型Eu(III)錯体の構造制御と光物性
平井悠一; 中西貴之; 関朋宏; 伊藤肇; 伏見公志; 長谷川靖哉, 光化学討論会要旨集(CD-ROM), 2014, ROMBUNNO.1B10, 2014
Japanese

金属錯体で架橋されたEu(III)錯体ポリマーの光物性
山本昌紀; 中西貴之; 関朋宏; 伊藤肇; 伏見公志; 長谷川靖哉, 光化学討論会要旨集(CD-ROM), 2014, ROMBUNNO.3P091, 2014
Japanese

ペプチド系抗生物質フェガノマイシンの生合成に関与する新規ペプチドライゲース
野池基義; 雄谷洸一; 佐々木郁雄; 丸山千登勢; 石川淳; 佐藤康治; 濱野吉十; 伊藤肇; 大利徹, 日本農芸化学会北海道支部講演会講演要旨, 2013, 24, 27 Nov. 2013
Japanese

微小な機械的刺激をトリガーとした金(I)イソシアニド錯体の単結晶‐単結晶相転移
櫻田健太; 室本麻衣; 関朋宏; 伊藤肇, 錯体化学会討論会講演要旨集, 63rd, 55, 15 Oct. 2013
Japanese

金(I)イソシニアド錯体のポリモルフィズムに基づく単一化合物白色発光
関朋宏; 榑沼紗也佳; 伊藤肇, 錯体化学会討論会講演要旨集, 63rd, 56, 15 Oct. 2013
Japanese

フッ素置換ピリジル二核金(I)イソシアニド錯体の結晶多形と多色発光特性
尾崎太一; 大倉拓真; 関朋宏; 伊藤肇, 錯体化学会討論会講演要旨集, 63rd, 302, 15 Oct. 2013
Japanese

Eu(III)配位複合体の組織構造と発光特性
平井悠一; 中西貴之; 関朋宏; 伊藤肇; 佐藤敏文; 伏見公志; 長谷川靖哉, 錯体化学会討論会講演要旨集, 63rd, 292, 15 Oct. 2013
Japanese

九核Tb(III)クラスターの構造と光磁気機能の解明
鈴木勇喜; 土井貴弘; 日夏幸雄; 関朋宏; 伊藤肇; 小泉均; 中西貴之; 伏見公志; 長谷川靖哉, 錯体化学会討論会講演要旨集, 63rd, 138, 15 Oct. 2013
Japanese

光磁気特性を示す九核Tb(III)クラスターのスピン構造解析
鈴木勇喜; 土井貴弘; 日夏幸雄; 関朋宏; 伊藤肇; 小泉均; 中西貴之; 伏見公志; 長谷川靖哉, 光化学討論会講演要旨集, 2013, 187, 07 Sep. 2013
Japanese

放線菌に見出した新規ペプチドライゲース
野池基義; 雄谷洸一; 佐々木郁雄; 丸山千登勢; 石川淳; 佐藤康治; 濱野吉十; 伊藤肇; 大利徹, 日本放線菌学会大会講演要旨集, 28th, 62, 05 Sep. 2013
Japanese

金錯体が示す分子ドミノ現象:微弱な機械的刺激をトリガーとした単結晶‐単結晶相転移
櫻田健太; 室本麻衣; 関朋宏; 伊藤肇, 万有生命科学振興国際交流財団札幌シンポジウム, 25th, 54, 06 Jul. 2013
Japanese

機械的刺激に誘起される金(I)イソシアニド錯体の単結晶‐単結晶相転移:金原子間相互作用の形成
室本麻衣; 関朋宏; 伊藤肇, 日本化学会講演予稿集, 93rd, 3, 819, 08 Mar. 2013
Japanese

機械的刺激に誘起される金(I)イソシアニド錯体の単結晶‐単結晶相転移:金原子間相互作用の消失
櫻田健太; 関朋宏; 伊藤肇, 日本化学会講演予稿集, 93rd, 3, 820, 08 Mar. 2013
Japanese

オリゴエチレングリコール鎖を有する金イソシアニド錯体の刺激応答性多色発光
川口皓奨; 関朋宏; 唐津孝; 北村彰英; 伊藤肇; 矢貝史樹, 日本化学会講演予稿集, 93rd, 3, 790, 08 Mar. 2013
Japanese

金(I)イソシアニド錯体の結晶多形共存に由来する固体白色発光
関朋宏; 伊藤肇, 日本化学会講演予稿集, 93rd, 2, 345, 08 Mar. 2013
Japanese

九核テルビウム(III)クラスターの磁気光学特性
中西貴之; 鈴木勇喜; 関朋宏; 土井貴弘; 伏見公志; 日夏幸雄; 伊藤肇; 長谷川靖哉, 配位化合物の光化学討論会講演要旨集, 25th, 54, 55, 2013
Japanese

九核Tb(III)クラスターの合成および磁気光学特性
鈴木勇喜; 土井貴弘; 日夏幸雄; 伊藤肇; 中西貴之; 伏見公志; 長谷川靖哉, 光化学討論会講演要旨集, 2012, 184, 07 Sep. 2012
Japanese

メタロセン含有Eu(III)錯体の電場応答発光
佐藤奈緒; 伊藤肇; 中西貴之; 伏見公志; 長谷川靖哉, 光化学討論会講演要旨集, 2012, 180, 07 Sep. 2012
Japanese

ナフチル金(I)イソシアニド錯体のクロミック発光特性の制御
関朋宏; 榑沼紗也佳; 伊藤肇, 錯体化学会討論会講演要旨集, 62nd, 265, 01 Sep. 2012
Japanese

テトラフルオロピリジル基を有する金(I)イソシアニド錯体の多様な発光クロミズム特性
尾崎太一; 大倉拓真; 関朋宏; 伊藤肇, 錯体化学会討論会講演要旨集, 62nd, 127, 01 Sep. 2012
Japanese

アリール金(I)イソシアニド錯体の構造変化と発光特性
室本麻衣; 関朋宏; 伊藤肇, 錯体化学会討論会講演要旨集, 62nd, 127, 01 Sep. 2012
Japanese

電場応答型Eu(III)錯体の発光特性評価
佐藤奈緒; 伊藤肇; 中西貴之; 伏見公志; 長谷川靖哉, 配位化合物の光化学討論会講演要旨集, 24th, 83-84, 06 Aug. 2012
Japanese

Tb(III)クラスターの合成と光磁気特性評価
鈴木勇喜; 土井貴弘; 日夏幸雄; 伊藤肇; 中西貴之; 伏見公志; 長谷川靖哉, 日本化学会講演予稿集, 92nd, 2, 470, 09 Mar. 2012
Japanese

Direct Enantio-Convergent Transformation of Racemic Substrates without Racemization or Symmetrization
Hajime Ito; Shun Kunii, SYNTHESIS-STUTTGART, 1, A6, A7, Jan. 2011
English, Others

求核的ホウ素-金属化学種の新展開 : 含ホウ素化合物の革新的合成法をもたらす新活性種
伊藤 肇, 化学と工業 = Chemistry and chemical industry, 61, 3, 224, 225, 01 Mar. 2008
有機ホウ素化合物は、有機合成における反応剤や機能性材料として重要な化合物であり、これらをより効率よく合成する新しい方法が求められている。これまでホウ素原子が求核的に作用するようなホウ素化反応は限られていたが、最近高い求核性をもつホウ素－金属化学種が生み出され、その反応が注目されている。, 日本化学会, Japanese

Boration of an alpha,beta-enone using a diboron promoted by a copper(I)-phosphine mixture catalyst
H Ito; H Yamanaka; J Tateiwa; A Hosomi, TETRAHEDRON LETTERS, 41, 35, 6821, 6825, Aug. 2000
English

有機ケイ素反応剤・中間体の新しい合成手法 (1999年の化学(1))
細見 彰; 伊藤 肇, 化学, 54, 1, 68, 69, Jan. 1999
化学同人, Japanese

Regio- and Stereoselective Synthesis of ^<13>C-Labeled D-rido-Phytosphingosine via SmI_2-Mediated C-C Formation with ^<13>C-Labeled Isocyanide
MURAKAMI M.; ITO H.; ITO Y., 希土類 = Rare earths, 30, 44, 45, 22 May 1997
Japanese

Preparation and Reactions of (Alkaneimidoyl)lanthanides
MURAKAMI M.; ITO H.; ITO Y., 希土類 = Rare earths, 28, 346, 347, 16 May 1996
Japanese

SYNTHESIS OF UNSYMMETRICAL ALPHA-DIKETONES VIA AUTOOXIDATION OF ALPHA-HYDROXY IMINES
M MURAKAMI; KOMOTO, I; H ITO; Y ITO, SYNLETT, 7, 511, 512, Jul. 1993
English, Introduction scientific journal

錯体化学 基礎から応用まで (エキスパート応用化学テキストシリーズ)
長谷川 靖哉; 伊藤 肇
講談社, Mar. 2014

Innovative Approaches to Mechanochemical Organic Synthesis: Our Recent Research
Hajime Ito
Lecture in Newcastle University, 28 Mar. 2024, English, Invited oral presentation
[Invited]

Mechanochemistry for efficient synthesis of organic and organometallic compounds
Hajime Ito
Lecture in Birmingham University, 28 Mar. 2024, English, Invited oral presentation
[Invited]

From Mechanochromism of Organometallic Crystals to Mechanochemical Organic Synthesis
Hajime Ito
BCA Spring Meeting 2024, 26 Mar. 2024, English
[Invited]

Innovative Approaches to Mechanochemical Organic Synthesis: Our Recent Research
Hajime Ito
Lecture in Nanjing University of Technology, 02 Mar. 2024, English, Invited oral presentation
[Invited]

Innovative Approaches to Mechanochemical Organic Synthesis: Our Recent Research
Hajime Ito
Lecture in Yangzhou University, 02 Mar. 2024, Invited oral presentation
[Invited]

Innovative Approaches to Mechanochemical Organic Synthesis: Our Recent Research
Hajime Ito
Lecture in Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, 01 Mar. 2024, English, Invited oral presentation

Innovative Approaches to Mechanochemical Organic Synthesis: Our Recent Research
Hajime Ito
Lecture in Peking University, 29 Feb. 2024, English, Invited oral presentation
[Invited]

Innovative Approaches to Mechanochemical Organic Synthesis: Our Recent Research
Hajime Ito
Lecture in University of Science and Technology of China, 28 Feb. 2024, English, Invited oral presentation
[Invited]

Innovative Approaches to Mechanochemical Organic Synthesis: Our Recent Research
Hajime Ito
Lecture in Nanjing University, 27 Feb. 2024, English, Invited oral presentation
[Invited]

Innovative Approaches to Mechanochemical Organic Synthesis: Our Recent Research
Hajime Ito
Lecture in Chengdu Institute of Biology Chinese Academy of Sciences, 26 Feb. 2024, English, Invited oral presentation
[Invited]

Innovative Approaches to Mechanochemical Organic Synthesis: Our Recent Research
Hajime Ito
Lecture in University of Science and Technology of China, 26 Feb. 2024, English, Invited oral presentation
[Invited]

Innovative Approaches to Mechanochemical Organic Synthesis: Our Recent Research
Hajime Ito
Lecture in Sichuan University, 24 Feb. 2024, English, Invited oral presentation
[Invited]

Revolutionizing Organic Synthesis: Unlocking Efficiency with Mechanochemical Reactions
Hajime Ito
International Symposium on Catalysis and Fine Chemicals 2023, 05 Dec. 2023, English, Invited oral presentation
[Invited]

Organic Synthesis through Piezoelectric Materials as Mechanoredox Catalysis
Hajime Ito
The 13th Asian Meeting on Ferroelectrics jointly with the 13th Asian Meeting on Electroceramics (AMF-13 & AMEC-13), 15 Nov. 2023, English, Invited oral presentation
[Invited]

From Mechanochromism Discovery to Advancements in Mechanochemical Organic Synthesis
Hajime Ito
116th CEMS Colloquium, 25 Oct. 2023, English, Invited oral presentation
[Invited]

メカノケミストリーの最近の発展とこれから
伊藤 肇
第13回CSJ化学フェスタ・メカノケミストリーの最前線～叩け！揺らせ！ちぎれ！～, 19 Oct. 2023, English, Keynote oral presentation
[Invited]

Mechanochemical Organic Synthesis and Creation of Complex Organosilicon Compounds
Hajime Ito
List Research Platform Kickoff Symposium, 10 Oct. 2023, English, Invited oral presentation
[Invited]

Mechanically Induced Structural Transformations in Luminescent Gold Complexes
Hajime Ito
26TH CONGRESS AND GENERAL ASSEMBLY OF THE INTERNATIONAL UNION OF CRYSTALLOGRAPHY, 29 Aug. 2023, English, Invited oral presentation
[Invited]

Iterative Synthesis of Oligosilanes Using Methoxyphenyl- or Hydrogen-Substituted Silylboronates as Building Blocks: A General Synthetic Method for Complex Oligosilane
伊藤 肇
第8回けむすい論文対談, 21 Aug. 2023, Japanese, Others
[Invited]

Mechanochemical Synthesis of Organometallic Compounds
Hajime Ito
21st International Symposium on Organometallic Chemistry Directed Toward Organic Synthesis (OMCOS 21), 25 Jul. 2023, English, Invited oral presentation
[Invited]

Design and Optimization of Mechanochemical Reactions: Exploring New Horizons in Organic Synthesis
Hajime Ito
The 80th Anniversary International Symposium on Organic Synthesis, 20 Jul. 2023, English, Invited oral presentation
[Invited]

発光性メカノクロミズムからメカノケミカル有機合成へ
伊藤肇
第55回有機金属若手の会夏の学校, 04 Jul. 2023, English, Invited oral presentation
[Invited]

Developing mechanoredox catalysis as a green alternative to photoredox reactions
Hajime Ito
27th Annual Green Chemistry & Engineering Conference, 12 Jun. 2023, English, Invited oral presentation
[Invited]

Exploring the Frontiers of Mechanochemistry: Innovative Strategies for Developing New Organic Reactions
Hajime Ito
Lecture in Strasbourg University, 19 May 2023, English, Invited oral presentation
[Invited]

メカノケミカル有機合成の新展開
伊藤 肇
第72回高分子学会年次大会, 19 May 2023, English, Invited oral presentation
[Invited]

Catalysis design for mechanochemical organic synthesis
Hajime Ito
The 2nd Newcastle Mechanochemistry Symposium (NMS-2), 16 May 2023, English, Invited oral presentation
[Invited]

メカノケミカル有機合成の新展開と特徴
伊藤 肇
第132回触媒討論会, 2023, English, Invited oral presentation
[Invited]

「銅触媒による有機ホウ素化合物の新合成法とメカノ応答性をもつ発光性金錯体の開発」
伊藤 肇
日本化学会第94春季年会, 27 Mar. 2014, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Mechano-Triggered Single-Crystal-to-Single-Crystal Transformation of Gold(I) Isocyanide Complexes
ITO Hajime
The 12th Conference of the Asian Crystallographic Association (AsCA13), 07 Dec. 2013, English, Invited oral presentation
[Invited], [International presentation]

Luminescent Mechanochromism and Single-Crystal to Single-Crystal Phase Transformation of Gold(I) Isocyanide Complexes
ITO Hajime
2nd International Conference on Mechanoluminescence and Novel Structural Health Diagnosis (ML-2), 10 Nov. 2013, English, Invited oral presentation
[Invited], [International presentation]

「発光性アリール金イソシアニド錯体：機械的刺激によって誘起される単結晶-単結晶相転移」
伊藤 肇
第22回有機結晶シンポジウム, 30 Oct. 2013, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

「有機ホウ素化合物の新しい合成方法：銅触媒と塩基活性化剤」
伊藤 肇
第53回オーロラセミナー, 21 Jul. 2013, Japanese, Public discourse
[Invited]

「金イソシアニド錯体の結晶構造と発光特性：メカノ結晶工学への手がかり」
伊藤 肇
平成25年度 有機合成セミナー, 13 Jul. 2013, Japanese, Public discourse
[Invited]

「有機ホウ素化合物の新しい合成方法：ごく最近の知見」
伊藤 肇
平成25年度 前期（春季）有機合成化学講習会, 19 Jun. 2013, Japanese, Public discourse
[Invited]

「金イソシアニド錯体の結晶構造と発光特性：分子ドミノ」
伊藤 肇
分子研シンポジウム2013, 31 May 2013, Japanese, Public discourse
[Invited]

「有機金(I)錯体における微小な機械的刺激をトリガーにした単結晶－単結晶相転移」
伊藤 肇
物講研談話会, 13 May 2013, Japanese, Public discourse
[Invited]

“Formal Nucleophilic Boryl Substitution of Alkyl- and Aryl Halides in the Presence of Copper(I) Catalyst or Base Promoter ”
伊藤 肇
UK/Japan Conference in Catalytic Asymmetric Synthesis, 19 Apr. 2013, English, Invited oral presentation
[Invited], [International presentation]

大学院共通授業科目（一般科目）：自然科学・応用科学, 2024年, 修士課程, 大学院共通科目

応用化学特別講義, 2024年, 修士課程, 総合化学院

超分子化学, 2024年, 修士課程, 総合化学院

分子化学Ａ（有機金属化学), 2024年, 修士課程, 総合化学院

実践的計算化学, 2024年, 修士課程, 総合化学院

大学院共通授業科目（一般科目）：自然科学・応用科学, 2024年, 修士課程, 大学院共通科目

有機化学特論, 2024年, 修士課程, 総合化学院

先端総合化学特論Ⅱ, 2024年, 博士後期課程, 総合化学院

有機化学Ⅱ, 2024年, 学士課程, 工学部

工学特別講義, 2024年, 学士課程, 工学部

Sep. 2010 - Present
The Society of Polymer Science, Japan

Apr. 1999 - Present
近畿化学協会

Apr. 1999 - Present
有機合成化学協会

Jul. 1998 - Present
アメリカ化学会

Feb. 1992 - Present
日本化学会

Precise Synthesis of Asymmetric Organosilicon Compounds Using Functionalized and Asymmetric Silylboranes
Grants-in-Aid for Scientific Research
Apr. 2022 - Mar. 2026
伊藤 肇; 関 朋宏; 久保田 浩司; 陳 旻究; 高見澤 聡
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (A), Hokkaido University, 22H00318

Development of molecular crystals of catalytic engines driven by chemical reactions
Grants-in-Aid for Scientific Research
Jun. 2022 - Mar. 2025
伊藤 肇; 石山 竜生; 陳 旻究; 関 朋宏; 高見澤 聡
Japan Society for the Promotion of Science, Grant-in-Aid for Challenging Research (Pioneering), Hokkaido University, 22K18333

レドックスメカノケミストリーによる固体有機合成化学
戦略的創造研究推進事業
Oct. 2019 - Mar. 2025
科学技術振興機構, Principal investigator

Asymmetric Borylation with Chiral Dense Reaction Space
Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (A)
01 Apr. 2018 - 31 Mar. 2022
Ito Hajime
Aiming to establish a new guideline for catalyst development in asymmetric synthetic reactions, this study successfully developed catalysts that can precisely control the selectivity of reaction substrates based on the concept of "asymmetric tight-lattice reaction space". Based on the QuinoxP* ligand, the substituent pattern on phosphorus was successfully designed with the aid of computational chemistry. We also reported a novel approach to control the steric environment by introducing silicon substituents into the backbone. We also succeeded in synthesizing many new optically active organoboron compounds, and developed mechanochemical synthesis.
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (A), Hokkaido University, 18H03907

Mechanistic Study and New Function of Soft Crystals with Molecular Domino Phase Change
Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
30 Jun. 2017 - 31 Mar. 2022
Ito Hajime
This research was conducted to extend the function and elucidate the mechanism of soft crystals, which have properties intermediate between crystals, solids, and liquid crystals. As new soft crystals, we have successfully developed crystals with jumping properties and elucidated their mechanisms upon external stimuli. They also succeeded in developing luminescent amphiphilic dynamic crystals and a luminescent ferroelastic complex crystal with rotational part at the molecular level within the crystal. Furthermore, inspired by the study of soft crystals, wee discovered many new mechanochemical organic synthetic reactions.
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area), Hokkaido University, 17H06370

Synthesis of boron-containing organic materials by novel nucleophilic borylation
Grants-in-Aid for Scientific Research Grant-in-Aid for Challenging Exploratory Research
01 Apr. 2015 - 31 Mar. 2017
ITO Hajime
Organoboron compounds are vital synthetic intermediates for many organic transformations such as Suzuki coupling. Organoboron compounds are also important for organic materials. The researcher previously developed silyl boron/base reaction system for their efficient synthesis. In this research, the reaction has been expanded by the mechanistic insight obtained by calculation studies. New synthetic procedures for hetero-aromatic organoboron compounds, functionalized organoboron compounds, triaryl boron compounds have been developed.
Japan Society for the Promotion of Science, Grant-in-Aid for Challenging Exploratory Research, Hokkaido University, Principal investigator, Competitive research funding, 15K13633

Synthesis of boron-containing organic materials by novel nucleophilic borylation
Grants-in-Aid for Scientific Research
2015 - 2017
Ito Hajime
In this research, by using copper-catalyzed reactions and base-mediated reactions, we developed many useful synthetic reactions of organoboron compounds: alkyl-, alkenyl-, aryl, alkynyl halides, ketones, aldehydes, indole, pyridine, quinoline derivatives were applied to the boryl substitution reaction, boryl addition reaction, boryl cyclization reactions, dearomative borylations. We also develop asymmetric catalytic borylation through applying chiral catalysts to some of these new reactions. This research project afforded a significant amount of results of the development of many synthetic reactions of organoboron compounds, which are useful reagents on organic synthesis.
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (B), Hokkaido University, Principal investigator, Competitive research funding, 15H03804

Investigation of Mechanism on Spontaneous Single Crystal Phase Change Triggered by Small Mechanical Stress
Grants-in-Aid for Scientific Research
2014 - 2014
ITO Hajime; SEKI Tomohiro
Several gold-isocyanide complexes with various structures were synthesized and
investigated in detail. The directions of molecule arrangements in the new crystal phases generated by the small mechanical stress were random. The crystal structure and their phase direction of the crystal before the phase change did not influence the direction of the new crystal phase. We also found a new luminescent mechanochromic material with four different colors. We further discover a new gold-isocyanide complex that can undergo single-crystal-to-single-crystal phase change by irradiation of UV light. This complex shows a photosalient property.
Japan Society for the Promotion of Science, Grant-in-Aid for Challenging Exploratory Research, Hokkaido University, Principal investigator, Competitive research funding, 26620053

力学刺激応答材料の合理的機能デザイン
科学研究費補助金(新学術領域研究(研究領域提案型))
2011 - 2011
伊藤 肇
文部科学省, 新学術領域研究(研究領域提案型), 北海道大学, Principal investigator, Competitive research funding, 23107501

直接エナンチオ収束法を用いた光学活性化合物の合成
科学研究費補助金(基盤研究(A))
2011 - 2011
伊藤 肇
文部科学省, 基盤研究(A), 北海道大学, Principal investigator, Competitive research funding, 23245019

機械的刺激による発光スイッチングを利用したメカノ記録材料の研究
科学研究費補助金(挑戦的萌芽研究)
2010 - 2010
伊藤 肇
本研究では、機械的刺激によりUV照射下でのフォトルミネッセンスが変化する化合物「メカノクロミック化合物」の単結晶の表面に、AFMなどを用いて微小な機械的刺激を与え、極小のピット(機械的な加工痕)を作成し、その発光性の変化の検出が可能であるかを検証することを目的として研究をおこなった。研究の第一段階として、我々がすでに報告しているメカノクロミック化合物に加えて、よりこの目的に適した化合物の合成、開発を検討した。すなわち機械的刺激に敏感かつ、小領域での刺激であっても明瞭な判別が可能なスペクトル変化を与える化合物の合成を行った。新たな一般的合成法の検討の結果、塩化金イソシアニド錯体に対して、アリール有機金属(リチウム、マグネシウム、亜鉛)を反応させることで、さまざまなアリール金(I)イソシアニド錯体が合成可能であることが明らかになた。また、それらのメカノメカノクロミズム特性を調べたところ、オリジナル錯体で観察された青から黄色への発光色の変化だけではなく、緑からオレンジなどの変化を示す化合物をデザインできることが明らかになった。これらの発光性メカノクロミック化合物の単結晶に対しAFM装置のカンチレバーを利用して、ミクロンからナノサイズの書き込み(機械的刺激)を行い、微小ピットを作成し、蛍光顕微鏡によるその発光性の変化の観察、SEMによる観察、AFMによる表面の観察を行った。その結果、微小な機械的ピットの作成(20×20ナノメートル)が可能であることがわかった。サブミクロンサイズの比較的大きなピットでは、ピットにおける発光性の変化が観察できた。
文部科学省, 挑戦的萌芽研究, 北海道大学, Principal investigator, Competitive research funding, 22655058

Asymmetric Catalytic Synthesis of Optically Active Organoboron Compounds with Chiral Borylcopper Species
Grants-in-Aid for Scientific Research(基盤研究(B))
2008 - 2010
Hajime ITO
Novel methods for efficient synthesis of optically active organoboron compounds with chiral copper(I)-catalyst have been developed. The reactions, which include copper(I) salts and chiral phosphine ligands, promote various borylation reaction to produce optically active organoboron compounds with high enantioselectivity. This method enables the asymmetric catalytic synthesis of unprecedented chiral cyclopropyl-, ally- and homoallyboronates, which will facilitate the synthesis of intermediates for medicines.
Ministry of Education, Culture, Sports, Science and Technology, 基盤研究(B), 北海道大学, Principal investigator, Competitive research funding, 20350043

多核金錯体による発光性ネットワーク構造の合成とトライボクロミズムの研究
科学研究費補助金(特定領域研究)
2008 - 2009
伊藤 肇
本研究では、金(I)-イソシアニド錯体が、顕著な発光性メカノクロミズム特性を有していることを明らかにした。この錯体は乳鉢中ですりつぶすなどの機械的刺激により、そのフォトルミネッセンスが大きく変化する上、発光性が変化した錯体を溶媒にさらすことで、容易にもとの発光状態へ戻すことが可能である。また、この現象のメカニズムについて考察を行った。今年度は、メカノクロミズム特性を持つ化合物を水中に分散してできる有機ナノ結晶が、単価結晶状態、溶液状態とは大きく異なる発光特性を有することを明らかにした。また、単結晶にたいして、AFMを用いて刺激を加えることにより、ミクロサイズのスクラッチが形成でき、さらにこのスクラッチ痕が発光性の変化として観察できることを明らかにした。この化合物は、こする前の状態では青色発光を示す微結晶であり、これにすりつぶすという機械的刺激を加えることにより、アモルファス状態へと変化する性質を持つ。青色発光を示す微結晶では、π-πスタッキングによる分子間相互作用が支配的であるが、アモルファス状態では、おそらく、金原子間同士の弱い結合が形成され、これを介した分子間相互作用が支配的になると考えられる。溶媒を加えると再結晶がおこり、熱力学的に安定なもとの青色発光を示す状態に戻る。この現象は、配位子に含まれるフッ素原子の小さい分子間力により、分子同士のずれが起こりやすくなり、機械的刺激による固体相の変化が誘起されやすくなっていることが一つの要因であると推測される。熱分析などの結果からは、この機械的刺激によってもとの状態より高いエネルギー状態のメタ安定状態が形成されていることが示唆された。
文部科学省, 特定領域研究, 北海道大学, Principal investigator, Competitive research funding, 20036003

発光性メカノクロミックプローブの開発
ＪＳＴ戦略的創造研究推進制度（個人研究型） （個人研究推進事業：さきがけ研究２１‐ＰＲＥＳＴＯ）
2008
Competitive research funding

多核金-イソシアニド錯体を用いた発光性ネットワーク構造の合成
科学研究費補助金(特定領域研究)
2007 - 2007
伊藤 肇
「発光性メカノクロミズム」とは、ある化合物に対して機械的刺激を与えたときに、その発光性が変化する性質のことである。このような性質を持つ化合物は、力学感知センサーや記録材料として幅広い応用が期待できる。しかし、この「発光性メカノクロミズム」特性をもつ化合物の合成例はごく限られていた。報告者は、金(I)錯体の多くが固体、室温でも強い発光性を示すことに着目して研究を行い、二核金(I)-イソシアニド錯体(I)が、この発光性メカノクロミズム特性を有していることを明らかにした。この錯体は乳鉢中ですりつぶすなどの機械的刺激により、そのフォトルミネッセンスが大きく変化する上、発光性が変化した錯体を溶媒にさらすことで、容易にもとの発光状態へ戻すことが可能である。また、吸収スペクトル、発光スペクトル測定および、エックス線構造解析、粉末X線回折(PXRD)、IRなどからこの現象のメカニズムを考察した。金(I)錯体では、金同士の弱い相互作用が形成される場合があり、その結果特徴的な発光性を示すことが知られている。この錯体の場合、機械的刺激で、金(I)原子間の相互作用が誘起されるものと考えられる。金(I)錯体の中でも、特にこの錯体がメカノクロミズムを示す理由については、今後詳細な研究が必要となるが、配位子に含まれるフッ素原子の小さい分子間力により、分子同士のずれが起こりやすくなり、機械的刺激による固体相の変化が誘起されやすくなっていることが一つの要因であると推測される。
文部科学省, 特定領域研究, 北海道大学, Principal investigator, Competitive research funding, 19027003

Selective Synthesis through Dehydrogenative Silylation with Optically Active Gold(I) Complex
Grants-in-Aid for Scientific Research(基盤研究(C))
2006 - 2007
Hajime ITO
Efficient synthesis of optically active compounds is important issue in organic synthesis. In addition, development of new reactions for efficient utilization of resources and reduction of wastes have become very important subject. In this study, the new methods involving kinetic resolution of chiral alcohols through dehydrogenative silylation with optically active gold(I) complexes were examined.As a preliminary experiment, xantphos-type ligands that have different steric bulk were prepared and the gold(I)-catalyzed dehydrogenative silylation with these ligands was studied. The sterically hindered ligands showed high activities. Next, kinetic resolutions of chiral alcohols were tested by using chiral phosphine ligands. Although the optically active alcohols were obtained, the enantiomeric purities of the resultant products were low.In order to develop more efficient gold(I) catalysts for kinetic resolution, synthesis and characterization of a gold(I) hydride compound, which is expected to be a key intermediate of catalysis, were investigated. Although gold(I) hydride compounds had never been characterized in solution before, the researcher found that the gold hydride secrecies were generated in the gold(I)-catalyzed dehydrogenative silylation of alcohols. The gold(I) hydride species were characterized by H, P, C, NMR and ESI-Mass.
Ministry of Education, Culture, Sports, Science and Technology, 基盤研究(C), 北海道大学, Principal investigator, Competitive research funding, 18550088

11族金属錯体を用いた新規触媒反応の設計と有機合成反応の探索
科学研究費助成事業
2000 - 2001
細見 彰; 伊藤 肇; 三浦 勝清; 北條 信; 立岩 淳一
本研究課題で今年度得られた成果を以下に示す。
(1)11族金属が触媒として作用する新反応を見つけだし、有機合成的に実用的な反応を目指し,11族金属が関与する反応の反応機構を実験的かつ理論的に明確にし、さらなる新反応開発のための知見を得た。
(2)銅(I)塩錯体と13,14族化合物などとの組み合わせによる新規反応の開発した。
極く最近、銅(I)塩錯体と有機ケイ素化合物が極性溶媒中でスムーズにメタセシス反応が進行することを見つけ、本反応の一般性を確立し、さらに、有機ケイ素と同じ14族元素であるスズ、ゲルマニウムなどの他の有機金属化合物との反応性を調べ、新しい合成反応を見つけ、速報としてその一部を速報として報告した。その際、新規銅(I)塩錯体を合成、検討することで各反応に対して最適な触媒の開発を行った。また同様に有機スズ化合物、有機ホウ素化合物などの13,15族元素を含む化合物についても研究を行った。
(3)銅触媒を用いる金属-金属結合間のメタセシス反応および金(I)錯体と13族及び14族化合物との反応探索と金(I)塩錯体を触媒とする新規有機合成反応の開発した。
銅(I)塩を触媒とした金属-金属結合の生成反応を開発する。銅(I)触媒の特異な反応性を利用して、ケイ素-水素結合間の組み替え、ケイ素-スズ結合間の組み替えなど、合成法として有用と思われる新規触媒反応の発見を目指した。さらにメタセシス反応を利用したケイ素、スズなどを含む有機金属ポリマーの新規合成法を見つける。さらに、金(I)錯体は銅(I)錯体と同様に一価と三価のredoxサイクルを有しているので、金(I)錯体においても13,14族有機金属化合物との反応を調べ、新しい合成反応を見つけた。
(4)非局在電子系を有する有機分子の新規合成法の開発した。
新たに見つけたケイ素-銅交換反応によるカップリング反応と、従来のPd触媒を用いるStilleカップリング等との基質選択性の違いを組み合わせて利用することで、非局在電子系を有する有機分子の「オルソゴナル合成法」を確立し、おもに非局在電子系をもつ芳香環やヘテロ環からなる有機分子の簡便かつ効率の良い合成手法を見つけた。
日本学術振興会, 萌芽的研究, 筑波大学, 12875174

11族金属を利用した新触媒反応の計算化学および実験化学的探索
科学研究費補助金(特定領域研究(A))
2000 - 2001
伊藤 肇; 永田 央; 永田 央; 伊藤 肇
後周期遷移金属化合物を触媒とする反応は、有機合成化学的に非常に有用であり、これまで多くの実験的研究が行われている。また、その反応機構を知ることは、触媒反応の設計上重要なことから、計算科学的な研究も非常に盛んである。われわれは、最近、11族金属を触媒とする有機合成反応を新たに開発し、成果を上げている。その一連の研究の中で、金(I)錯体を用いたヒドロシリル化反応を発見した。金(I)錯体は、後周期遷移金属からなる錯体でありながら、有機合成反応の触媒として使われた例は非常に少なかった。最近、われわれが発見した例を含めて、金錯体触媒が、有用な触媒として働くこと例が報告されている。しかしこれまで、金錯体を用いた触媒反応を計算化学的に考察した例はない。われわれは、自分たちが発見した金(I)錯体の触媒反応の計算化学的研究を行い、その結果、金(I)錯体を用いる触媒反応に対する有益な知見を得た。金ヒドリド錯体、アルデヒド、ヒドロシランの出発系から比較して遷移状態Aの活性化エネルギーは+15.8kcal/molであった。この付加反応のあと、金アルコキシド錯体が形成されるが、その生成エネルギーは原系に対して26.1kcal/mol安定である。次の金アルコキシド錯体とヒドロシランの反応の遷移状態Bは原系に対して-16.5kcal/mol安定であり、反応前の金アルコキシド錯体とヒドロシランからの活性化エネルギーは+9.6kcal/molとなる。この反応の結果、原料であるアルデヒドがヒドロシリル化されたシリルエーテルが生成し、同時に触媒活性種である金ヒドリド錯体が再生し触媒サイクルが一巡する。この触媒1サイクルに伴う全生成エネルギーは50.1kcal/molである。これまで実験的な研究例が少なかった金(I)錯体の触媒反応について、始めて計算化学的な考察を行った。金(I)錯体を用いた触媒反応の研究はようやく始まったばかりであり、今回の反応も含めて、反応機構の研究は少ない。触媒反応に関する過去の蓄積が金(I)錯体ではあまりなく、また他の反応に参考を求めることができない今回のような反応では、金(I)錯体が、この反応の途中でどのような中間体・遷移状態をとり、どのようなエネルギー変化を取りながら触媒サイクルが進行するかは、計算化学の方法を用いることで始めてわかることであった。今回得られた成果は、さらに高度な反応の設計に役に立つことが予想できる。
文部科学省, 特定領域研究(A), 岡崎国立共同研究機構, Principal investigator, Competitive research funding, 12042284

New Syntheses of Highly Reactive and Functional Organometallic Compounds and its Application to Organic Syntheses
Grants-in-Aid for Scientific Research
1999 - 2001
HOSOMI Akira; ITO Hajime; MIURA Katsukiyo; HOJO Makoto; TOMINAGA Yoshiori; TATEIWA Jun-ichi
The following results are obtained in this research project.
Acid-Catalyzed Cyclization ofVinylsilanes Bearing an Amino Group. Stereoselective Synthesis ofPyrrolidines
In the presence of an acid catalyst, vinylsilanes bearing an amino group protected by an electron-withdrawing group were smoothly bychzed to 2-(silylmethyl) pyrrolidines. This cyclization was utilized for the Stereoselective synthesis of 2 ndisubstituted pyrrqlidines (n = 3-5).
Radical Cyclization of 1-6-Enynes Using Allylstannanes and New Radical Reactions Using Stannyl Enolates as Radical Transfer Agents
In the presence of AEBN, allyltributylstannanes bearing a radical-stabilizing group at the β-position smoothly reacted with 1,6-enynes to give cyclized products incorporated with the stannyl and allyl groups in moderate to good yields This cyclization is valuable for the synthesis of highly functionalized 5-membered carbocycles and heterocycles The reactions with β-cyanoallylstannane formed a certain amount of bicyclo[4.3.0]non-l-enes along with monocyclized products. The radicaHmtiated reactions of α-halo-esters, -nitriles, and -ketones with stannyl enolates gave the corresponding γ-keto denvatives in moderate to high yields. This homolytic process was applied to the three-component coupling reaction among stannyl enolates, haloalkanes, and electron-deficient alkenes.
Silicon-directed Cyclization of Vinylysilanes : Stereoselective Synthesis of Tetrahydrofurans and Tetrahydropyrans
Silicon-directed Stereoselective syn addition of hydroxy group to olefmic double bond occurs intramolecularly in an acid-catalyzed cyclization of vinylsilanes bearing hydroxy group. The cyclization proceeds by stereospecific syn addition of the hydroxy group Vinylsilanes, (Z)-5-silyl-4-penten-l-ols bearing a substituent on the methylene tether, smoothly undergo the acid-catalyzed cyclization to give trans-2,5-, cis-2,4-, and trans-2,3-disubstituted tetrahydrofurans respectively, with moderate to high stereoselectivitv.
Manganese Ate Species: Generation,and Reactions with Electrophiles
Trialkylmanganese (II) ate reagents, "RMnLi" reacted with iodomethylsulfides to produce thiomethylmanganese reagents, where the manganate serves as a reductant not an alkylation agent. The reductive behavior of trialkylmanganese (II) ate reagents provides a protocol for the direct generation of a new class of reagents thiomethylmanganese reagents with structural variety, and the generated thiomethylmanganese reagents reacted with allyl bromides, enones and aldehydes.
New Method for Introduction of a Silyl Group into α,β-Enones Using a Disilane Catalyzed by a Copper(I) salt.
The reaction of a disilane with a Cu(I) salt efficiently induces cleavage of the Si-Si bond to generate a silyl nucleophile in aprotic polar solvent and its 1,4-addition to α,β-unsaturated enones smoothly proceeds with a catalytic amount of a Cu(I) salt were found. This reaction is successfully applied to hexamethyldisilane to generate a trimethylsilyl nucleophile hitherto not easily accessible.
Unprecedented Manganese-Mediated Reactions : Generation of Non-Stabilized Carbonyl Ylids.
Activated manganese generates nonstabilized carbonyl ylides from bis (chloromethyl) ethers as a precursor, and using this system with manganese as a reductant, the reactions of the ylides with electron-deficient dipolarophiles can be attained without the direct reduction of dipolarophiles by the reductant.
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (B), University of Tsukuba, 11554029

11族金属錯体を用いた新規触媒的有機合成反応の開発とその理論的研究
科学研究費補助金(奨励研究(A))
1999 - 2000
伊藤 肇
後周期遷移金属化合物と有機ケイ素化合物との組み合わせにより,これまで多くの有用な有機合成反応が開発されている。例えば,ヒドロシランなどの有機ケイ素化合物は8,9,10族などの後周期遷移金属化合物に対する反応が知られており,これを利用してヒドロシリル化などの触媒的合成反応が数多く開発されてきた。しかし,銅(I)塩などの11族金属化合物と有機ケイ素化合物の反応例は少なく,これらを触媒とする合成反応の研究も限られていた。我々は最近、ヒドロシランやジシランのような有機ケイ素化合物を用い、銅(I)塩を触媒とする有用な合成反応を見いだした。さらに、銅(I)塩触媒による、有機ホウ素化合物を用いた触媒反応の開発もおこなった。また,同じ11族金属化合物である金(I)錯体を用いた触媒反応の開発にも成功し,これまで極めて例の少なかった金(I)錯体による触媒反応の新しい設計指針が得られた。Si-Si結合を持つ化合物と銅(I)塩との反応:銅(I)塩によりジシランが切断されることを初めて発見し、銅(I)塩触媒を用いたジシランによるα,β-エノンの共役シリル化反応を開発した。類似の反応は、過去にPd,Ni触媒でも報告されているが、銅(I)触媒を用いたこの反応は、ジシランに対する反応活性がより高く、合成反応としての一般性に優れている。(b)Si-H結合を持つ化合物と銅(I)塩の反応:ヒドロシランと銅(I)塩がDMI中で反応することを初めて明らかにした。さらにこれを利用してα,β-不飽和カルボニル化合物の選択的1,4-還元反応を開発した。
文部科学省, 奨励研究(A), 筑波大学->岡崎国立共同研究機構, Principal investigator, Competitive research funding, 11750732

New Syntheses of Highly Reactive and Functional Organometallic Compounds and its Application to Organic Syntheses
Grants-in-Aid for Scientific Research
1998 - 2000
HOSOMI Akira; ITO Hajime; MIURA Katsukiyo; HOJO Makoto; TATEIWA Jun-ichi
The following results are obtained in this research project.
1. Silicon-directed Cyclization of Vinylysilanes : Stereoselective Synthesis of Tetrahydrofurans and Tetrahydropyrans
Silicon-directed stereoselective syn addition of hydroxy group to olefinic double bond occurs intramolecularly in an acid-catalyzed cyclization of vinylsilanes bearing hydroxy group. The cyclization proceeds by stereospecific syn addition of the hydroxy group. Vinylsilanes, (Z)-5-silyl-4-penten-1-ols bearing a substituent on the methylene tether, smoothly undergo the acid-catalyzed cyclization to give trans-2,5-, cis-2,4-, and trans-2,3-disubstituted tetrahydrofurans, respectively, with moderate to high stereoselectivity.
2. Acid-Catalyzed Cyclization of Vinylsilanes Bearing an Amino Group. Stereoselective Synthesis of Pyrrolidines
In the presence of an acid catalyst, vinylsilanes bearing an amino group protected by an electron-withdrawing group were smoothly cyclized to 2-(silylmethyl) pyrrolidines. This cyclization was utilized for the stereoselective synthesis of 2, n-disubstituted pyrrolidines (n=3-5).
3. Unprecedented Manganese-Mediated Reactions : Generation of Non-Stabilized Carbonyl Ylids
Activated manganese generates nonstabilized carbonyl ylides from bis (chloromethyl) ethers as a precursor, and using this system with manganese as a reductant, the reactions of the ylides with electron-deficient dipolarophiles can be attained without the direct reduction of dipolarophiles by the reductant.
4. Manganese Ate Species : Generation and Reactions with Electrophiles
Trialkylmanganese (II) ate reagents, "R_3MnLi" reacted with iodomethylsulfides to produce thiomethylmanganese reagents, where the manganate serves as a reductant not an alkylation agent.
The reductive behavior of trialkylmanganese (II) ate reagents provides aprotocol for the direct generation of a new class of reagents, thiomethylmanganese reagents with structural variety, and the generated thiomethylmanganese reagents reacted with allyl bromides, enones and aldehydes.
5. Radical Cyclization of 1,6-Enynes Using Allylstannanes and New Radical Reactions Using Stannyl Enolates as Radical Transfer Agents
In the presence of AIBN, allyltributylstannanes bearing a radical-stabilizing group at the β-position smoothly reacted with 1,6-enynes to give cyclized products incorporated with the stannyl and allyl groups in moderate to good yields. This cyclization is valuable for the synthesis of highly functionalized 5-membered carbocycles and heterocycles. The reactions with β-cyanoallylstannane formed a certain amount of bicyclo [4.3.0] non-1-enes along with monocyclized products. The radical-initiated reactions of α-halo-esters, -nitriles, and -ketones with stannyl enolates gave the corresponding γ-keto derivatives in moderate to high yields. This homolytic process was applied to the three-component coupling reaction among stannyl enolates, haloalkanes, and electron-deficient alkenes.
6. New Method for Introduction of a Silyl Group into α, β-Enones Using a Disilane Catalyzed by a Copper (I) salt.
The reaction of a disilane with a Cu (I) salt efficiently induces cleavage of the Si-Si bond to generate a silyl nucleophile in an aprotic polar solvent and its 1,4-addition to α, β-unsaturated enones smoothly proceeds with a catalytic amount of a Cu (I) salt were found. This reaction is successfully applied to hexamethyldisilane to generate a trimethylsilyl nucleophile, hitherto not easily accessible.
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (B)., University of Tsukuba, 10450334

高配位遷移金属化合物の新規生成と関連化合物を用いる新反応の開発
科学研究費助成事業
1998 - 1999
細見 彰; 伊藤 肇; 三浦 勝清; 北條 信; 立岩 淳一
本研究課題で前年度に引き続き、今年度得られた成果を以下に示す。
(1)サマリウム外希土類金属カルベノイドの新規生成と反応性の解明および新規1,3-脱離反応による非安定化Tailor-madeカルボニルイリドとその関連活性種の生成と反応に関する研究を行った。
既知の方法で生成するカルボニルイリドは構造を安定化する置換基や官能基を有するものに限られており、これらの反応性には電荷が分離した性質が強く反応してくる。真のカルボニルイリドの性質を知るために下式に示した1,3-脱離反応によるカルボニルイリドの生成法は有力な手段となる。母体のカルボニルイリドを始め、任意の置換基を有するカルボニルイリドの生成法を明かにした。これらの反応性の全容を解明することも可能となる。金属によっては"1,3-dipolaroide"としてカルボニルイリドの反応性を制御できる可能性もあるため、用いる金属と生成するカルボニルイリドの反応性の関係についてもかなりの研究成果を得た。
(2)アリルスタニル化やアリルシリル化などラジカル反応を用いる立体選択的な新規萌芽的研究を行った。
(3)ビニルシランの新規酸触媒環化反応と含酸素環状化合物の高立体選択的合成反応を開発した。
(4)高配位マンガンおよびクロム化合物の反応性の解明と新規高配位マンガン、クロム他反応剤の創製と合成に関する研究を行った。
(a)高配位マンガン、クロム中間体(M=Mn,Cr)を得、その構造と反応性の関係を明らかにする努力を行った。
(b)高反応性高配位鉄、マンガン、クロム反応剤の創製とその反応の高次制御を行った。アリルアニオン、ヒドリドイオン、ビニルアニオンなど高反応性活性種の等価体として高配位遷移金属化合物を設計合成した。
(c)有機クロムアート化合物を用いる還元的メタル化反応を達成した。
(d)有機クロムおよび関連アート反応剤による不斉還元、アルキル反応およびジアステレオ選択的反応を見つけた。
また、中心金属(M=Mn Cr,Fe)、配位子、反応系の効果を検討した。さらに新しい還元剤の開発を目指した。
日本学術振興会, 萌芽的研究, 筑波大学, 10874106

低原子価金属塩を用いる有機ケイ素化合物の活性化と反応
科学研究費補助金(奨励研究(A))
1997 - 1998
伊藤 肇
1. シリルエノールエーテルの銅(I)塩による選択的アシル化:ケイ素・銅交換反応がシリルエノールエーテル上でも進行することを利用して,シリルエノールエーテルの銅(I)塩による選択的O-アシル化を行ったところ,広範な基質に対して良好な収率で目的物が得られた.2. 銅(I)触媒によるα,β一不飽和力ルボニル化合物の求核的シリル化:ケイ素求核剤はクロロシランやジシランからアルカリ金属を用いて還元するなどの方法で発生することができるが,炭素求核剤と比べると比較的発生させにくいことからやや敬遠されがちであった.われわれはケイ素-ケイ素結合が銅(I)塩で切断されることを初めて発見し,これを利用して求核的なケイ素化剤を触媒的に発生させる方法を見つけた.1〜10%触媒量のCU(I)OTfの存在下,ジシランがα,β-不飽和カルボニル化合物に1,4-付加反応し,引き続く酸加水分解により,β-シリル化体が高収率で得られることを新たに見いだした.この反応は銅塩に対する配位子の効果が顕著で,銅(I)塩に対して小過剰のトリブチルホスフィンの添加により収率が向上する.また溶媒としてはDMFがもっともよい結果を与える.基質としてはα,β-不飽和アルデヒドも可能であるが,α,β-不飽和エステルの場合は収率が低下する.ジシランのα,β-不飽和ケトンへの1,4-付加反応はPd触媒を用いた報告があるが,ハロゲン置換により活性化されたジシランが必要であるなど制限があり,この銅(I)塩触媒を用いる方法の方が一般性は高い.3. 光学活性ヒドロシランにおけるケイ素・銅(I)交換:光学活性ヒドロシランにおいて,ケイ素・銅(I)交換反応に基づくシリルエーテル合成を行ったところ,極性溶媒中にもかかわらず,ケイ素上の立体が保持された生成物が得られた.このことはこのケイ素・銅交換反応を経由する反応機構の考察に有益な示唆を与える.
文部科学省, 奨励研究(A), 筑波大学, Principal investigator, Competitive research funding, 09750929

マンガンアート錯体および関連有機金属化合物を用いる新反応の展開
科学研究費助成事業
1997 - 1997
細見 彰; 伊藤 肇; 三浦 勝清; 北條 信
本研究課題で今年度得られた成果を以下に示す.
ヨウ化ビニルあるいはアセチレンから生じるビニルラジカルが,分子間での立体選択的炭素-炭素結合生成に有効であることが明らかとなった.また,イオン的反応として知られていたアリルメタル化反応がラジカル機構でも進行することを示し,精密有機合成におけるラジカル反応の適用範囲をいっそう広げることができた.
また,有機マンガンアート錯体の生成とその反応挙動はこれまで殆ど知られておらず,その詳細を明らかにすることにより,今後有機合成上重要な有機金属試剤となり得ることを明らかにした.α-位に還元され得る酸素官能基を有するケトンに対して有機マンガンアート化合物を反応することにより,マンガンエノラートが直接的に得られることを見つけた.得られたエノラートに対してアルデヒドを作用させることにより,アルドール誘導体が高収率で得られた.また,生成したマンガンエノラートは種々の求電子剤と反応して対応する置換生成物を高収率で与えた.
さらに,有機マンガンアート化合物はアリルブロミド,プロパルギルブロミドとの反応により,還元的メタル化を起し,対応するアリルマンガンアート反応剤,および,プロパルギルマンガンアート反応剤を高収率で与えることを見付けた.この際,有機マンガンアート化合物の有機リガンドとして,テトラブチルマンガナ-ト錯体が好都合であった.
日本学術振興会, 萌芽的研究, 筑波大学, 09875224

実践的有機金属反応剤の開発と天然物指向有機合成への新展開
科学研究費助成事業
1997 - 1997
細見 彰; 伊藤 肇; 三浦 勝清; 北條 信
多官能性有機金属化合物の合成設計と新反応およびその合成化学への応用を目指した研究の一環として,(1)合成化学的に重要であるが反応性が高いために十分に活用されていない反応活性種である有機ラジカルを用いるあたらしい.立体選択的な有機合成反応を見つけた.ラジカル開始剤存在下アルケンとアリルスタナンを反応させれば,スタニルラジカルのアルケンへの付加および生成するアルキルラジカルのアリル化により,ラジカル的アリルスタニル化の初めての例を見つけた. さらに、アルキンとの反応においてもアリルスタニル化が効率的にかつこう立体選択的に進行することを見つけた。(2)サマリウムを用いる新反応を開発する目的で非安定化カルボニルイリドの生成と新規反応を見つけた.ビス(クロロメチルエーテル)に2価サマリウムを作用させることによりカルボニルイリドが生成し,カルボニル化合物存在下に行うとジオキソランが,また,アルケン類およびアルキン類共存下では高収率で対応するテトラヒドロフラン類とジヒドロフラン類が生成することを見つけた.本反応により世界で始めて全く置換基を持たない母体のカルボニルイリドを得ることができたばかりでなく,"Taior-made" のカルボニルイリドを自由に得る方法を明らかにできた.(3)有機マンガンアート錯体を新規電子移動型還元剤として用いるアリル銅種およびマンガンエノラートの新規生成反応を見つけた.(4)分子内の適当な位置に水酸基のような求核剤を有するビニルシランを用いたところ,プロトンやLewis酸触媒による反応によって生じるβ-シリル炭素陽イオン中間体が,1,2-ケイ素転移を伴い,水酸基と反応して,テトラヒドロフランやテトラヒドロピラン誘導体などの含酸素環状化合物を立体選択的に効率よく与えることを見つけた.
日本学術振興会, 重点領域研究, 筑波大学, 09231206

高配位構造を有する金属活性種と高次触媒体の構築に関する合成化学研究
科学研究費助成事業
1997 - 1997
細見 彰; 伊藤 肇; 三浦 勝清; 北条 信
精密有機合成では有機溶媒に可溶な酸触媒がよく利用されているが,有機溶媒に不溶な固体酸触媒を用いる不均一反応についてはあまり研究されていない.反応の後処理,触媒の回収,再利用が容易であるという点から見れば,固体酸触媒の関与する反応系の構築は重要な課題である.本研究では,含酸素ヘテロ環類の立体選択的合成を目指して,粘土鉱物やヘテロポリ酸類のような固体酸を触媒として用いるビニルシラン類の環化反応について検討した.水酸基を有するビニルシラン類の環化反応では,粘土鉱物やヘテロポリ酸のような固体酸触媒を利用できることがわかった.しかし,これらの固体酸(12モリブドリン酸を除く)を用いる不均一反応はр-トルエンスルホン酸や四塩化チタンを用いる均一反応に比べると反応時間,環化効率の面でまだまだ問題が多い.均一系触媒に匹敵する活性を有する固体酸触媒の探索を続け,固体酸触媒を用いる反応の立体選択性についてより詳細に検討した.ビニルシラン,固体酸を用いて、クロロホルム(2.5mL)中,室温で行った.酸触媒にはまず市販品であるナトリウムモンモリロナイト(クニピア),活性白土,モンモリロナイトK10を用いて反応を行った.その結果,酸性度が低いナトリウムモンモリロナイトでは,原料回収に終わったが,シリケート層間の交換性陽イオンがプロトンである活性白土やモンモリロナイトK10では環化反応が効率よく進行することがわかった.交換性陽イオンがアルミニウム,チタン,セリウム,亜鉛であるモンモリロナイトは向山アルドール反応,Friedel-Crafts反応,カルボニル化合物のアセタール化などの触媒として有用であることが知られているが,この反応においても触媒活性を示した.
日本学術振興会, 重点領域研究, 筑波大学, 09218209

New Reactions Using Highly Functional Organometallic Compounds and its Application to Synthetic Chemistry
Grants-in-Aid for Scientific Research
1996 - 1997
HOSOMI Akira; ITO Hajime; MIURA Katsukiyo; HOJO Makoto
The following results are obtained in this research project.
1.Silicon-directed Cyclization of Vinylysilanes : Stereoselective Synthesis of Tetrahydrofuranes and Tetrahydropyranes
Silicon-directed stereoselective syn addition of hydroxy group to olefinic double bond occurs intramolecularly in an acid-catalyzed cyclization of vinylsilanes bearing hydroxy group. Thus 5-dimethylphenylsilyl-4-penten-1-ol is smoothly cyclized to 2- (dimethylphenylsilyl) methyltetrahydrofuran upon the treatment of a catalytic amount of p-toluenesulfonic acid (TsOH) or TiCl_4.
2.Unprecedented Samarium-Mediated Reactions : Generation of Non-Stabilized Carbonyl Ylids
Samarium reveals a strong reducing ability and by virtue of this character together with its oxophilicity, is widely applied to organic synthesis in the formation of carbon-carbon bonds and transformation of a variety of functionalities with high selectivities. In the course of our study on the generation and reactions of reactive species, we report herein the generation of novel active species, non-stabilized carbonyl ylids from iodomethyl silyl ethers mediated by samarium, otherwise inaccessible, and their [3+2] cycloadditions to a variety of unsaturated compounds such as aldehydes, alkenes, allenes, and alkynes.
3.Manganese AteSpecies : Generation and Reactions with Electrophiles
Tetrabutylmanganese ate complex 'Bu_4MnLi_2' reacts with allylic and prop-2-ynylic bromides to generate the corresponding allyl-and prop-2-ynyl-manganese species which further react with electrophiles such as aldehydes, ketones, epoxide, and chlorosilanes to afford the corresponding allylated and prop-2-ynylated and/or allenylated products in high yields.
4.Allylstannylation of Alkynes and Alkenes via a Radical Process : Stereoselective Synthesis of Di-and Tri-Substituted Vinylstannanes
In the presence of AIBN,allylstannanes bearing an electron-withdrawing group at the beta-position easily reacted with terminal and electron-deficient internal alkynes to give beta-allyl-substituted vinylstannanes in moderate to good yields. The allylstannylation proceeds with anti addition exclusively. Allylstannanes bearing an electron-withdrawing group at the beta-position easily reacted with various electron-deficient alkenes to introduce both the allyl and stannyl groups.
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (B), University of Tsukuba, 08454228

Creation of Highly Functional Reagents and its Application to Novel Organic Synthesis
Grants-in-Aid for Scientific Research
1995 - 1997
HOSOMI Akira; TOMINAGA Yoshinori; HAYASHI Nobuyuki; ITO Hajime; MIURA Katsukiyo; HOJO Makoto; DHOGANE Iwao
The following results are obtained in this research project.
1.Manganese Ate Complexes as a New Reducing Agent : Perfectly Regiocontrolled Generation and Reactions of the Mn-Enolates with Electrophiles
Manganese (II) ate complexes cleanly react with carbonyl compounds bearing a leaving group at the alpha position to generate the enolates of the original ketones, esters, and amides, irrespective of their structure, where the manganate serves as a reductant not an alkylation agent. In this reductive generation of the enolates based on the novel reactivity of the manganese ate complexes, a kind of oxidative addition of a substrate to the ate complex and the reductive elimination of the ligands on manganese are possibly involved as the key processes, while the process equivalent to "metal-halogen exchange" does not seem to be significant. The generality of this reaction was demonstrated in the generation of the enolates of not only aromatic ketones and aliphatic ketones but also an aliphatic ester and amide. As for the synthetic value, this reaction was successfully applied to the perfectly regiospecific generation and reactions of a pair of the regioisomeric enolates corresponding to the unsymmetrical and non-branched aliphatic ketones.
2.Unprecedented Samarium-Mediated Reactions : Generation of Non-Stabilized Carbonyl Ylids
Samarium reveals a strong reducing ability and by virtue of this character together with its oxophilicity, is widely applied to organic synthesis in the formation of carbon-carbon bonds and transformation of a variety of functionalities with high selectivities. In the course of our study on the generation and reactions of reactive species, we report herein the generation of novel active species, non-stabilized carbonyl ylids from iodomethyl silyl ethers mediated by samarium, otherwise inaccessible, and their [3+2] cycloadditions to a variety of unsaturated compounds such as aldehydes, alkenes, allenes, and alkynes.
3.Silicon-Directed Cyclization of Vinylsilanes Bearing Hydroxy Group Catalyzed by an Acid
The acid-catalyzed cyclization of vinylsilanes bearing a hydroxy group took place cleanly to give tetrahydrofurans and tetrahydropyrans, and the addition of hydroxy group to vinylsilane proceeded in a syn stereoselective fashion.
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (A), University of Tsukuba, 07555276

実践的有機金属反応剤の開発と天然物指向有機合成への新展開
科学研究費助成事業
1996 - 1996
細見 彰; 伊藤 肇; 三浦 勝清; 北條 信
本研究では,1)有機マンガンアート化合物の電子移動型還元挙動の解明と新規ケトンエノラートの位置特異的生成反応の開発を行った.特に,遷移金属は種々の酸化数を取り得るために遷移金属化合物は中心金属が合成化学的に有用な酸化・還元的性質を示す.これらの高配位有機金属化合物の化学の新たな展開を目指して中心金属をマンガン金属とした有機マンガンアート化合物の,特にその電子移動型還元挙動を明らかにするとともに,新しいケトンエノラートの位置特異的生成反応の開発を行った.
有機マンガンアート錯体の生成とその反応挙動はこれまで殆ど知られておらず,その詳細を明らかにすることにより,今後有機合成上重要な有機金属試剤となり得る.α-位に還元され得る酸素官能基を有するケトンに対して有機マンガンアート化合物を反応することにより,マンガンエノラートが直接的に得られることを見つけた.得られたエノラートに対してアルデヒドを作用させることにより,アルドール誘導体が高収率で得られた.また,生成したマンガンエノラートは種々の求電子剤と反応して対応する置換生成物を高収率で与えた.
2)有機銅アート錯体を新規電子移動型還元剤として用いるアリル銅種の生成と反応を研究したところ,ケテンジチオアセタール類に電子吸引基が置換した場合に効率よくビニル銅種が生成することを示した.また,クロロ基を脱離基とするケテンジチオアセタール類を用いて有機銅アート錯体との反応を検討したところ,電子移動を含む還元的メタル化により新規アリル銅種が効率よく生成することを見つけた.官能基を持つアリル銅種を他の方法では得難いので,本方法は新しい官能基置換の有用な合成法を見つけたことになる.
日本学術振興会, 重点領域研究, 筑波大学, 08245207

高配位構造を有する金属活性種と高次触媒系の構築に関する合成化学研究
科学研究費助成事業
1996 - 1996
細見 彰; 伊藤 肇; 三浦 勝清; 北條 信
シリル基がβ位の炭素陽イオンを安定化することはよく知られており,有機ケイ素化合物の反応性を理解する上で重要な特性の一つである.ビニルシランはα位でプロトンと反応し,β-シリル炭素陽イオンを中間体として与える.通常β-シリル炭素陽イオンからのシリル基の脱離は非常に速いため,この中間体を求核剤との反応に利用した例はほとんど知られていない.本研究では,分子内の適当な位置に水酸基のような求核剤を有するビニルシランを用いたところ,固体酸触媒によって生じるβ-シリル炭素陽イオン中間体が水酸基と反応して,テトラヒドロフランやテトラヒドロピラン誘導体などの含酸素環状化合物を効率よく与えた.酸触媒にはまず市販品であるナトリウムモンモリロナイト(クニピア),活性白土,モンモリロナイトK10を用いて反応した結果,酸性度が低いナトリウムモンモリロナイトでは原料回収に終わったが,シリケート層間の交換性陽イオンがプロトンである活性白土やモンモリロナイトK10では環化反応が効率よく進行することがわかった.交換性陽イオンがアルミニウム,チタン,セリウム,亜鉛であるモンモリロナイトが,この反応において触媒活性を示した.これら触媒系において超音波照射下での反応も試みたが,触媒活性の向上には効果的ではなかった.次に,12-タングストリン酸,12-モリブドリン酸,12-タングストケイ酸のようなヘテロポリ酸を用いて反応を行ったところ,これらのプロトン酸触媒も本環化反応に対して高い触媒活性を有することが明らかとなった.なお,12-モリブドリン酸は溶媒であるクロロホルムに可溶であり,このために触媒活性が著しく向上したものと考えられる.
日本学術振興会, 重点領域研究, 筑波大学, 08232213

希土類錯体を用いる反応活性種の生成と有機合成へ応用
科学研究費助成事業
1996 - 1996
北條 信; 伊藤 肇; 三浦 勝清; 細見 彰
サマリウム反応剤を用いる新規非安定化カルボニルイリドの生成と反応
サマリウムの関与する反応活性種として新規なカルボニルイリドの発生反応を見つけた.さらに発生するカルボニルイリドはこれまで生成例のないアルキル基のみが置換した非安定化カルボニルイリドである.これらは反応に際して高い反応性および選択性を示すことを明らかにした.(J.Am.Chem.Soc.,1996,118(14),3533-3534.)さらにビス(クロロメチル)エーテル類を前駆体とする非安定化カルボニルイリドの発生法を見つけ,無置換(母体)のカルボニルイリドの発生と反応に初めての例として成功した.無置換カルボニルイリドは立体的にも電子的にも安定化を受けていないために非常に高い反応性を示し,様々な炭素-炭素2重結合および3重結合,さらには芳香族化合物に対しても[3+2]環化付加を起こすことが明らかとなった.この発生法は必要な構造を有するカルボニルイリドを前駆体からデザイン-合成し,意のままに発生させることができる“Tailor-made"な発生法としても応用できることを実証した.これら一連の研究を通じて環化付加反応に際して発現する立体選択性をはじめとする各種選択性に関する多くの知見が初めて明らかとなった.(Tetrahedron Lett.,1996,37(51),9241-9244.)
日本学術振興会, 重点領域研究, 筑波大学, 08220209

高活性銅(I)錯体触媒の開発 有機ナノ構造体の合成
Competitive research funding

Development of Highly active Cu(I) catalysts Synthesis of organic nano-structure
Competitive research funding

プラスチック材料を開始剤とするラジカル反応の開発～医薬品や機能性材料をより安全で環境に優しく生産するための有機合成プロセスの開発へ～
25 Dec. 2023
北海道大学 PRESS RELEASE
北海道大学 PRESS RELEASE

The Ultimate Birch Reduction?
10 Apr. 2023
Other than myself
Science
Science
https://www.science.org/content/blog-post/ultimate-birch-reduction, [Paper]

空気下、室温で実施可能な超高速バーチ還元反応を開発～ボールミルを用いたメカノケミカル法により、従来の溶液合成の制限を克服～
05 Apr. 2023
Myself
北海道大学 PRESS RELEASE
北海道大学 PRESS RELEASE
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