猪熊　泰英 (イノクマ　ヤスヒデ)

工学研究院　応用化学部門　有機工業化学分野教授
創成研究機構化学反応創成研究拠点教授
Last Updated :2024/12/06

■研究者基本情報

学位

  • 博士（理学）, 京都大学, 2009年03月

Researchmap個人ページ

ホームページURL

J-Global ID

研究キーワード

  • カルボニル化合物
  • 超分子化学
  • ホストーゲスト化学
  • 細孔性錯体
  • X線結晶構造解析
  • 単結晶

研究分野

  • ナノテク・材料, 機能物性化学

■経歴

経歴

  • 2023年04月 - 現在
    北海道大学, 大学院工学院, 教授
  • 2016年04月 - 2023年03月
    北海道大学, 工学研究院, 准教授
  • 2014年03月 - 2016年03月
    東京大学, 工学(系)研究科(研究院), 講師
  • 2009年04月 - 2014年02月
    東京大学, 工学(系)研究科(研究院), 助教

学歴

  • 2004年04月 - 2009年03月, 京都大学大学院, 理学研究科, 化学専攻
  • 2000年04月 - 2004年03月, 京都大学, 理学部

委員歴

  • 2021年04月 - 現在
    JSTさきがけ「物質探索空間の拡大による未来材料の創製」領域, 領域アドバイザー, 学協会
  • 2015年 - 2020年
    錯体化学会, 将来計画委員, 学協会

■研究活動情報

受賞

  • 2024年03月, 日本化学会, 学術賞
    単分散ポリケトンに立脚した機能性有機分子の創出
    猪熊 泰英, 39951576
  • 2022年04月, 公益財団法人長瀬科学技術振興財団, 長瀬研究振興賞　　　　　　　　　　　　　　　
    猪熊 泰英
  • 2019年12月, Asian Chemical Congress, Asian Rising Stars Lectureship　　　　　　　　　　　　　　　
    Aliphatic polyketones for clay-play like molecular synthesis
    猪熊 泰英
  • 2019年04月, 田中貴金属記念財団, 「貴金属に関わる研究助成金」奨励賞　　　　　　　　　　　　　　　
    脂肪族ポリイミン化合物を基盤とする貴金属イオン吸着材料の開発
    猪熊泰英
  • 2016年04月, 東京大学大学院工学系研究科, 東京大学工学系研究科長表彰　　　　　　　　　　　　　　　
    猪熊泰英
  • 2015年09月, 一般財団法人 フロンティアサロン財団, 永瀬賞 特別賞　　　　　　　　　　　　　　　
    分子構造を捉える手法 「結晶スポンジ法」の開発
    猪熊泰英
  • 2015年04月, 文部科学省, 文部科学大臣表彰 若手科学者賞　　　　　　　　　　　　　　　
    細孔性結晶を用いた微量化合物のＸ線結晶構造解析法の研究
    猪熊泰英
  • 2014年12月, 科学技術・学術政策研究所 (NISTEP), ナイスステップな研究者2014　　　　　　　　　　　　　　　
    ごく微量の化合物や非結晶物質の精緻なＸ線構造解析を可能にする「結晶スポンジ法」の開発
    猪熊泰英
  • 2014年03月, 日本化学会, 進歩賞　　　　　　　　　　　　　　　
    細孔性錯体を用いた溶液化学のＸ線構造解析による可視化
    猪熊泰英
  • 2013年11月, 錯体化学会, 研究奨励賞　　　　　　　　　　　　　　　
    細孔性錯体を用いた結晶化を必要としない結晶構造解析法の開発
    猪熊泰英
  • 2013年03月, 英国王立化学会, PCCP賞　　　　　　　　　　　　　　　
    Nano-to-microgram scale X-ray crystallography of non-crystalline compounds using crystalline sponges
    猪熊泰英

論文

  • Molecular Dynamics‐Based Conformational Simulation Method for Analysis of Arrival Time Distributions in Ion Mobility Mass Spectrometry
    Keisuke Tashiro, Yuki Ide, Tetsuya Taketsugu, Kazuaki Ohara, Kentaro Yamaguchi, Masato Kobayashi, Yasuhide Inokuma
    Advanced Theory and Simulations, Wiley, 2024年07月27日
    研究論文（学術雑誌）, Abstract

    Ion mobility‐mass spectrometry (IM‐MS) has recently contributed to the structural analysis of molecules, including supramolecules and proteins, by determining the ion arrival time distributions correlated with the collision cross sections (CCSs), as well as the mass‐to‐charge ratios. However, its application range is still limited owing to the lack of general CCSs simulation methods based on possible molecular conformations. Here, a molecular dynamics‐based conformational search method for simulating CCS distributions using projection approximation is reported. As a case study, the gas‐phase conformations of the sodium adducts of conformationally flexible polyketones with 3,3‐dimethylpentane‐2,4‐dione as the monomer are analyzed. The sodium adduct of the hexamer (m/z 781.4 for [1 + Na]+) showed a monomodal arrival time distribution, but that of the octamer sodium adduct (m/z 1033.5 for [2 + Na]+) is multimodal. The conformational analysis indicated an unimodal CCS distribution of simulated [1 + Na]+ conformations in which the sodium cation is mainly bound at the chain terminal. Conversely, four clusters of conformations are obtained for [2 + Na]+ based on the Na+‐coordination sites, which qualitatively reproduced the observed CCS distribution. This approach will extend the utility of IM‐MS for the conformational analysis of flexible molecules in the gas phase.
  • Contracted porphyrins and calixpyrroles: synthetic challenges and ring-contraction effects.
    Keita Watanabe, Narendra Nath Pati, Yasuhide Inokuma
    Chemical science, 15, 19, 6994, 7009, 2024年05月15日, ［国際誌］
    英語, 研究論文（学術雑誌）, Ring-contracted porphyrin analogues, such as subporphyrins and calix[3]pyrroles, have recently attracted considerable attention not only as challenging synthetic targets but also as functional macrocyclic compounds. Although canonical porphyrins and calix[4]pyrrole are selectively generated via acid-catalyzed condensation reactions of pyrrole monomers, their tripyrrolic analogues are always missing under similar conditions. Recent progress in synthesis has shown that strain-controlled approaches using boron(iii)-templating, core-modification, or ring tightening provide access to various contracted porphyrins. The tripyrrolic macrocycles are a new class of functional macrocycles exhibiting unique ring-contraction effects, including strong boron chelation and strain-induced ring expansion. This Perspective reviews recent advances in synthetic strategies and the novel ring-contraction effects of subporphyrins, triphyrins(2.1.1), calix[3]pyrroles, and their analogous.
  • Drug-drug conjugates of MEK and Akt inhibitors for RAS-mutant cancers.
    Hikaru Fujita, Sachiko Arai, Hiroshi Arakawa, Kana Hamamoto, Toshiyuki Kato, Tsubasa Arai, Nanaka Nitta, Kazuki Hotta, Natsuko Hosokawa, Takako Ohbayashi, Chiaki Takahashi, Yasuhide Inokuma, Ikumi Tamai, Seiji Yano, Munetaka Kunishima, Yoshihiro Watanabe
    Bioorganic & medicinal chemistry, 102, 117674, 117674, 2024年03月15日, ［国際誌］
    英語, 研究論文（学術雑誌）, Controlling RAS mutant cancer progression remains a significant challenge in developing anticancer drugs. Whereas Ras G12C-covalent binders have received clinical approval, the emergence of further mutations, along with the activation of Ras-related proteins and signals, has led to resistance to Ras binders. To discover novel compounds to overcome this bottleneck, we focused on the concurrent and sustained blocking of two major signaling pathways downstream of Ras. To this end, we synthesized 25 drug-drug conjugates (DDCs) by combining the MEK inhibitor trametinib with Akt inhibitors using seven types of linkers with structural diversity. The DDCs were evaluated for their cell permeability/accumulation and ability to inhibit proliferation in RAS-mutant cell lines. A representative DDC was further evaluated for its effects on signaling proteins, induction of apoptosis-related proteins, and the stability of hepatic metabolic enzymes. These in vitro studies identified a series of DDCs, especially those containing a furan-based linker, with promising properties as agents for treating RAS-mutant cancers. Additionally, in vivo experiments in mice using the two selected DDCs revealed prolonged half-lives and anticancer efficacies comparable to those of trametinib. The PK profiles of trametinib and the Akt inhibitor were unified through the DDC formation. The DDCs developed in this study have potential as drug candidates for the broad inhibition of RAS-mutant cancers.
  • One‐pot, Gram‐Scale Synthesis of Calix[5]‐ and Calix[6]furan: Derivatization for Polyketone‐ and Isopyrazole‐based Macrocycles with Conformational Analysis
    Tomoki Yoneda, Taichi Sano, Narendra Nath Pati, Yuki Ide, Yasuhide Inokuma
    Asian Journal of Organic Chemistry, Wiley, 2024年02月29日
    研究論文（学術雑誌）, Abstract

    A gram‐scale synthesis of calix[5]‐ and calix[6]furan was achieved by a one‐pot condensation of furan and acetone followed by stepwise separation of calix[n]furans (n=4–6) using size‐selective precipitation procedures. Calix[n]furans were converted to cyclic polyketones and then to ethylene‐bridged cyclic isopyrazoles. The conformational analysis of the cyclic furan, polyketone, and isopyrazole macrocycles was performed based on their single crystal structures, providing important structural insights for intermolecular interactions. The scalable synthetic procedures for larger calix[n]furans and their derivatives would contribute to further coordination and host‐guest chemistry using their cavities.
  • Identifying high-grade serous ovarian carcinoma–specific extracellular vesicles by polyketone-coated nanowires
    Akira Yokoi, Mayu Ukai, Takao Yasui, Yasuhide Inokuma, Kim Hyeon-Deuk, Juntaro Matsuzaki, Kosuke Yoshida, Masami Kitagawa, Kunanon Chattrairat, Mikiko Iida, Taisuke Shimada, Yumehiro Manabe, I-Ya Chang, Eri Asano-Inami, Yoshihiro Koya, Akihiro Nawa, Kae Nakamura, Tohru Kiyono, Tomoyasu Kato, Akihiko Hirakawa, Yusuke Yoshioka, Takahiro Ochiya, Takeshi Hasegawa, Yoshinobu Baba, Yusuke Yamamoto, Hiroaki Kajiyama
    Science Advances, 9, 27, American Association for the Advancement of Science (AAAS), 2023年07月07日
    研究論文（学術雑誌）, Cancer cell–derived extracellular vesicles (EVs) have unique protein profiles, making them promising targets as disease biomarkers. High-grade serous ovarian carcinoma (HGSOC) is the deadly subtype of epithelial ovarian cancer, and we aimed to identify HGSOC-specific membrane proteins. Small EVs (sEVs) and medium/large EVs (m/lEVs) from cell lines or patient serum and ascites were analyzed by LC-MS/MS, revealing that both EV subtypes had unique proteomic characteristics. Multivalidation steps identified FRα, Claudin-3, and TACSTD2 as HGSOC-specific sEV proteins, but m/lEV-associated candidates were not identified. In addition, for using a simple-to-use microfluidic device for EV isolation, polyketone-coated nanowires (pNWs) were developed, which efficiently purify sEVs from biofluids. Multiplexed array assays of sEVs isolated by pNW showed specific detectability in cancer patients and predicted clinical status. In summary, the HGSOC-specific marker detection by pNW are a promising platform as clinical biomarkers, and these insights provide detailed proteomic aspects of diverse EVs in HGSOC patients.
  • Machine Learning-Based Analysis of Molar and Enantiomeric Ratios and Reaction Yields Using Images of Solid Mixtures
    Yuki Ide, Hayato Shirakura, Taichi Sano, Muthuchamy Murugavel, Yuya Inaba, Sheng Hu, Ichigaku Takigawa, Yasuhide Inokuma
    American Chemical Society (ACS), 2023年05月26日
    Visual observations are frequently used as a preliminary evaluation of the chemical contents of mixtures, but their accuracy largely depends on the observer’s experience and intuition, which are difficult to share. Here, we report component ratio pre-diction using image-based machine learning (ML), which is applicable to analysis of various solid mixtures, such as mix-tures of organics and inorganics, polymorphous crystals, and enantiomers. The trained model with 300 images could predict the sugar/dietary salt weight ratio from an image within 4% error. The ML prediction pipeline was shown to be broadly ap-plicable to polymorphic glycine, D/L-tartaric acid, and four-component systems. As an application demonstration, we also used our ML system to analyze yield of a solid-state decarboxylation reaction. These results demonstrated that accumulation of researchers’ experience derived from visual information can be shared as trained ML models and used as a quantitative analysis method.
  • The geometry of calix[3]pyrrole and the formation of the calix[3]pyrrole·F− complex in solution
    Ranajit Saha, Jenny Pirillo, Yuki Ide, Yasuhide Inokuma, Yuh Hijikata
    Theoretical Chemistry Accounts, 142, 5, Springer Science and Business Media LLC, 2023年04月26日
    研究論文（学術雑誌）
  • Chain-Length-Dependent Hydrogen-Bonded Self-Assembly of Terminally Functionalized Discrete Polyketones
    Kilingaru I. Shivakumar, Yumehiro Manabe, Tomoki Yoneda, Yuki Ide, Yasuhide Inokuma
    Precision Chemistry, 1, 1, 34, 39, American Chemical Society (ACS), 2023年03月09日, ［最終著者, 責任著者］
    研究論文（学術雑誌）
  • Chiral Calix[3]pyrrole Derivatives: Synthesis, Racemization Kinetics, and Ring Expansion to Calix[9]‐ and Calix[12]pyrrole Analogues
    Yuya Inaba, Jian Yang, Yu Kakibayashi, Tomoki Yoneda, Yuki Ide, Yuh Hijikata, Jenny Pirillo, Ranajit Saha, Jonathan L Sessler, Yasuhide Inokuma
    Angewandte Chemie International Edition, Wiley, 2023年02月13日, ［査読有り］, ［最終著者, 責任著者］
    英語, 研究論文（学術雑誌）
  • Toward calix[2]-type macrocycles: Synthesis and structural analysis of cyclic tetraketone and highly strained furanophane
    Taichi Sano, Yuhua Sun, Taichi Mukai, Yuya Inaba, Tomoki Yoneda, Yuki Ide, Jenny Pirillo, Yuh Hijikata, Yasuhide Inokuma
    Journal of Porphyrins and Phthalocyanines, World Scientific Pub Co Pte Ltd, 2023年01月21日, ［査読有り］, ［招待有り］, ［最終著者, 責任著者］
    英語, 研究論文（学術雑誌）
  • Carbonyl-Containing Solid Polymer Electrolyte Host Materials: Conduction and Coordination in Polyketone, Polyester, and Polycarbonate Systems.
    Therese Eriksson, Harish Gudla, Yumehiro Manabe, Tomoki Yoneda, Daniel Friesen, Chao Zhang, Yasuhide Inokuma, Daniel Brandell, Jonas Mindemark
    Macromolecules, 55, 24, 10940, 10949, 2022年12月27日, ［国際誌］
    英語, 研究論文（学術雑誌）, Research on solid polymer electrolytes (SPEs) is now moving beyond the realm of polyethers that have dominated the field for several decades. A promising alternative group of candidates for SPE host materials is carbonyl-containing polymers. In this work, SPE properties of three different types of carbonyl-coordinating polymers are compared: polycarbonates, polyesters, and polyketones. The investigated polymers were chosen to be as structurally similar as possible, with only the functional group being different, thereby giving direct insights into the role of the noncoordinating main-chain oxygens. As revealed by experimental measurements as well as molecular dynamics simulations, the polyketone possesses the lowest glass transition temperature, but the ion transport is limited by a high degree of crystallinity. The polycarbonate, on the other hand, displays a relatively low coordination strength but is instead limited by its low molecular flexibility. The polyester performs generally as an intermediate between the other two, which is reasonable when considering its structural relation to the alternatives. This work demonstrates that local changes in the coordinating environment of carbonyl-containing polymers can have a large effect on the overall ion conduction, thereby also showing that desired transport properties can be achieved by fine-tuning the polymer chemistry of carbonyl-containing systems.
  • Absorption spectra of calix[3]pyrrole analogs as probes for contracted macrocycles
    Keita Watanabe, Ranajit Saha, Yuya Inaba, Yumehiro Manabe, Tomoki Yoneda, Yuki Ide, Yuh Hijikata, Yasuhide Inokuma
    Journal of Porphyrins and Phthalocyanines, World Scientific Pub Co Pte Ltd, 2022年11月11日
    研究論文（学術雑誌）
  • Determination of the critical chain length for macromolecular crystallization using structurally flexible polyketones
    Yuki Ide, Yumehiro Manabe, Yuya Inaba, Yusuke Kinoshita, Jenny Pirillo, Yuh Hijikata, Tomoki Yoneda, Kilingaru I. Shivakumar, Saki Tanaka, Hitoshi Asakawa, Yasuhide Inokuma
    Chemical Science, 13, 34, 9848, 9854, Royal Society of Chemistry (RSC), 2022年09月, ［査読有り］, ［最終著者, 責任著者］
    英語, 研究論文（学術雑誌）, Critical chain length that divides small molecular crystallization from macromolecular crystallization is an important index in macro-organic chemistry to predict chain-length dependent properties of oligomers and polymers. However, extensive researches...
  • Alkali metal ion binding using cyclic polyketones
    Narito Ozawa, Kilingaru I. Shivakumar, Muthuchamy Murugavel, Yuya Inaba, Tomoki Yoneda, Yuki Ide, Jenny Pirillo, Yuh Hijikata, Yasuhide Inokuma
    Chemical Communications, 58, 18, 2971, 2974, Royal Society of Chemistry (RSC), 2022年03月, ［査読有り］, ［招待有り］, ［最終著者, 責任著者］
    英語, 研究論文（学術雑誌）, Cyclic oligoketones composed of 3,3-dimethylpentane-2,4-diones showed crown ether-like alkali metal ion binding behavoir with association constants up to 1.7 x 104 M–1 in chloroform/acetonitrile (v/v, 9/1). The binding properties have...
  • Strain‐induced Ring Expansion Reactions of Calix[3]pyrrole‐related Macrocycles
    Yuya Inaba, Yu Kakibayashi, Yuki Ide, Jenny Pirillo, Yuh Hijikata, Tomoki Yoneda, Yasuhide Inokuma
    Chemistry – A European Journal, 28, 17, Wiley, 2022年02月09日, ［査読有り］, ［最終著者, 責任著者］
    英語, 研究論文（学術雑誌）
  • Hybrid Eu III Coordination Luminophore Standing on Two Legs on Silica Nanoparticles for Enhanced Luminescence
    Teng Zhang, Yuichi Kitagawa, Ryoma Moriake, Pedro Paulo Ferreira da Rosa, Md. Jahidul Islam, Tomoki Yoneda, Yasuhide Inokuma, Koji Fushimi, Yasuchika Hasegawa
    Chemistry – A European Journal, 27, 58, 14438, 14443, Wiley, 2021年10月19日, ［査読有り］, ［国際誌］
    英語, 研究論文（学術雑誌）, In this study, we have demonstrated a two-legged, upright molecular design method for monochromatic and bright red luminescent LnIII -silica nanomaterials. A novel EuIII -silica hybrid nanoparticle was developed by using a doubly binding TPPO-Si(OEt)3 (TPPO: triphenyl phosphine oxide) linker. The TPPO-Si(OEt)3 was confirmed by 1 H, 31 P, 29 Si NMR spectroscopy and single-crystal X-ray analysis. Luminescent Eu(hfa)3 and Eu(tfc)3 moieties (hfa: hexafluoroacetylacetonate, tfc: 3-(trifluoromethylhydroxymethylene)camphorate) were fixed onto TPPO-Si(OEt)3 -modified silica nanoparticles, producing Eu(hfa)3 (TPPO-Si)2 -SiO2 and Eu(tfc)3 (TPPO-Si)2 -SiO2 , respectively. Eu(hfa)3 (TPPO-Si)2 -SiO2 exhibited the higher intrinsic luminescence quantum yield (93 %) and longer emission lifetime (0.98 ms), which is much larger than those of previously reported EuIII -based hybrid materials. Eu(tfc)3 (TPPO-Si)2 -SiO2 showed an extra-large intrinsic emission quantum yield (54 %), although the emission quantum yield for the precursor Eu(tfc)3 (TPPO-Si(OEt)3 )2 was found to be 39 %. These results confirmed that the TPPO-Si(OEt)3 linker is a promising candidate for development of EuIII -based luminescent materials.
  • Polyketone-Based Molecular Ropes as Versatile Components for Functional Materials
    Yasuhide Inokuma, Yuya Inaba
    Bulletin of the Chemical Society of Japan, 94, 9, 2187, 2194, The Chemical Society of Japan, 2021年09月15日, ［査読有り］, ［招待有り］
    研究論文（学術雑誌）
  • Isopyrazole‐Masked Tetraketone: Tautomerism and Functionalization for Fluorescent Metal Ligands
    Hayato Shirakura, Yumehiro Manabe, Chika Kasai, Yuya Inaba, Makoto Tsurui, Yuichi Kitagawa, Yasuchika Hasegawa, Tomoki Yoneda, Yuki Ide, Yasuhide Inokuma
    European Journal of Organic Chemistry, 2021, 30, 4345, 4349, Wiley, 2021年08月13日, ［査読有り］, ［最終著者, 責任著者］
    英語, 研究論文（学術雑誌）
  • Calix[3]pyrrole: A Missing Link in Porphyrin-Related Chemistry
    Yuya Inaba, Yu Nomata, Yuki Ide, Jenny Pirillo, Yuh Hijikata, Tomoki Yoneda, Atsuhiro Osuka, Jonathan L. Sessler, Yasuhide Inokuma
    Journal of the American Chemical Society, 143, 31, 12355, 12360, American Chemical Society (ACS), 2021年08月11日, ［査読有り］, ［最終著者, 責任著者］
    英語, 研究論文（学術雑誌）
  • Insoluble π‐Conjugated Polyimine as an Organic Adsorbent for Group 10 Metal Ions
    Hayato Shirakura, Yuh Hijikata, Jenny Pirillo, Tomoki Yoneda, Yumehiro Manabe, Muthuchamy Murugavel, Yuki Ide, Yasuhide Inokuma
    European Journal of Inorganic Chemistry, 2021, 17, 1705, 1708, Wiley, 2021年05月07日, ［査読有り］, ［最終著者, 責任著者］
    英語, 研究論文（学術雑誌）, Metal ion adsorbents are indispensable materials for the recovery of noble metal ions in a sustainable society. Herein, we report that poly(isopyrazole-3,5-diyl-trans-vinylene) (1) effectively adsorbed group 10 metal ions from solution in acetonitrile. Owing to its fully pi-conjugated and rigid structure, polyimine 1 was virtually insoluble in common organic solvents and water, making it advantageous for metal ion adsorption via a solid/liquid interface. Inductively coupled plasma (ICP) analysis showed that >= 90 % of Ni2+, Pd2+, and Pt2+ ions were adsorbed at a concentration of 10 mu M (order of <= 2 ppm) after stirring suspensions at room temperature. Metal ion desorption was achieved by treatment with ethylenediaminetetraacetic acid disodium salt (EDTA . 2Na), and the adsorbent was reused. Theoretical calculations supported that the desolvation energy was an important factor for effective adsorption in acetonitrile.
  • Spirosilicate dimers of a bowl-shaped diol generated by intramolecular cyclization of an aliphatic tetraketone chains
    Yuya Inaba, Yasuhide Inokuma
    Chemistry Letters, 49, 882, 884, The Chemical Society of Japan, 2020年05月13日, ［査読有り］, ［最終著者, 責任著者］
    研究論文（学術雑誌）
  • Modular synthesis of oligoacetylacetones via site-selective silylation of acetylacetone derivatives　　　　　　　　　　　　　　　
    Parantap Sarkar, Yuya Inaba, Hayato Shirakura, Tomoki Yoneda, Yasuhide Inokuma
    Organic & Biomolecular Chemistry, 18, 3297, 3302, 2020年04月, ［査読有り］, ［最終著者, 責任著者］
    英語, 研究論文（学術雑誌）
  • Supramolecular Conformational Control of Aliphatic Oligoketones by Rotaxane Formation
    Yumehiro Manabe, Keisuke Wada, Yudai Baba, Tomoki Yoneda, Tomoki Ogoshi, Yasuhide Inokuma, Yumehiro Manabe, Keisuke Wada, Yudai Baba, Tomoki Yoneda, Tomoki Ogoshi, Yasuhide Inokuma
    Organic Letters, 2020, 22, 3224, 3228, AMER CHEMICAL SOC, 2020年04月, ［査読有り］, ［最終著者, 責任著者］
    英語, 研究論文（学術雑誌）, Conformational control of aliphatic oligoketones bearing two 1,3-diketone subunits is achieved by molecular recognition with pillar[5]arene. Pillar[S]arene binds to aliphatic ketones, with association constants K of similar to 10 M-1, to form pseudorotaxanes. The pseudorotaxanes are locked by BF, complexation at the 1,3-diketone sites through quasi-solid-state reactions. X-ray crystallography reveals linear conformations for the axis molecules. The effect of supramolecular conformational restriction is evaluated using an alkyl-linked dyad chromophore system that shows solvatochromism upon intramolecular aggregation.
  • Chiral Monolayers with Achiral Tetrapod Molecules on Highly Oriented Pyrolytic Graphite
    Hitoshi Asakawa, Sayaka Matsui, Quang Thang Trinh, Hajime Hirao, Yasuhide Inokuma, Tomoki Ogoshi, Saki Tanaka, Kayo Komatsu, Akio Ohta, Tsuyoshi Asakawa, Takeshi Fukuma
    Journal of Physical Chemistry C, 124, 14, 7760, 7767, 2020年04月, ［査読有り］
    研究論文（学術雑誌）, Copyright © 2020 American Chemical Society. The self-assembly of organic molecules at the surface of highly oriented pyrolytic graphite (HOPG) is a promising process for constructing molecular-scale architectures. However, selectable organic molecules are generally restricted to two-dimensional molecules with planar Ï-conjugated structures and alkyl chains. We herein present the formation of self-assembled monolayers of tetrakis(4-ethynylphenyl)methane (TEPM) having a three-dimensional (3D) tetrapod geometry on HOPG, which was achieved by utilizing a simple spin-coating method. The arrangements of TEPM molecules in the monolayers were investigated using frequency-modulation atomic force microscopy (FM-AFM). The resulting subnanometer-resolution FM-AFM images revealed that the TEPM molecules formed linear rows with a periodicity of 0.85 nm oriented in a parallel configuration but with two alternating intervals of 0.7 and 1.0 nm. Moreover, the TEPM monolayers were classified into two chiral types with a relationship of mutual mirror-image symmetry, according to the observed molecular arrangements. Our results demonstrate the capability of TEPM molecules to act as 3D building blocks for the design of molecular-scale architectures at interfaces.
  • Polyketones as Host Materials for Solid Polymer Electrolytes
    Therese Eriksson, Amber Mace, Yumehiro Manabe, Masahiro Yoshizawa-Fujita, Yasuhide Inokuma, Daniel Brandell, Jonas Mindemark
    Journal of The Electrochemical Society, 167, 7, 070537, 070537, The Electrochemical Society, 2020年03月13日
    研究論文（学術雑誌）
  • Identification of Actinomycin D as a Specific Inhibitor of the Alternative Pathway of Peptidoglycan Biosynthesis
    Yasushi Ogasawara, Yohei Shimizu, Yohei Sato, Tomoki Yoneda, Yasuhide Inokuma, Tohru Dairi
    The Journal of Antibiotics, 73, 2, 125, 127, NATURE PUBLISHING GROUP, 2020年, ［査読有り］
    英語, 研究論文（学術雑誌）, Peptidoglycan is an indispensable component of bacterial cell walls. We recently discovered an alternative peptidoglycan biosynthetic pathway, which involves two enzymes, MurD2 and MurL, catalyzing the ligation of l-Glu to UDP-MurNAc-l-Ala and epimerization of the terminal l-Glu of the MurD2 product, respectively. Because the pathway operates in Xanthomonas oryze, a pathogen causing bacterial blight of rice, we searched for specific inhibitors from metabolites produced by actinomycetes to obtain a lead compound to function as an agrochemical. Actinomycin D was isolated from Streptomyces parvulus NBRC 13193 as a specific inhibitor of the pathway. In vitro analysis indicated that actinomycin D inhibited the MurD2 reaction.
  • Aliphatic polyketones as classic yet new molecular ropes for structural diversity in organic synthesis
    Yasuhide Inokuma, Tomoki Yoneda, Yuki Ide, Shota Yoshioka
    Chemical Communications, 56, 64, 9079, 9093, Royal Society of Chemistry (RSC), 2020年, ［査読有り］, ［筆頭著者, 責任著者］
    英語, 研究論文（学術雑誌）,

    Synthesis, reactivity, and recent chemistry developments regarding aliphatic polyketones are highlighted with respect to chain sequences. These classic compounds are still showing new research potentials.

  • Luminescent Coordination Polymers Constructed from Flexible, Tetradentate Diisopyrazole Ligand and Copper(I) Halides
    Tomoki Yoneda, Chika Kasai, Yumehiro Manabe, Makoto Tsurui, Yuichi Kitagawa, Yasuchika Hasegawa, Parantap Sarkar, Yasuhide Inokuma
    Chemistry–An Asian Journal, 15, 5, 601, 605, WILEY-V C H VERLAG GMBH, 2020年, ［査読有り］, ［責任著者］
    英語, 研究論文（学術雑誌）, One- and two-dimensional coordination polymers composed of a structurally flexible, tetradentate diisopyrazole ligand and copper(I) halides were synthesized as crystalline solids. Complexation with copper(I) chloride or bromide resulted in the formation of infinite coordination chains through connecting each diisopyrazole ligand with two copper(I) ions in a trigonal planar coordination geometry. Contrarily, the combination of a diisopyrazole ligand and copper(I) iodide gave a two-dimensional coordination network comprising Cu4I4 units with stair-step type geometry and diisopyrazoles that acted as both tetradentate and bidentate bridging ligands. All the coordination polymers exhibited visible photo-emission upon UV irradiation, and the Cu4I4 complex showed thermochromic behavior.
  • Splitting and Reorientation of π-Conjugation by an Unprecedented Photo-Rearrangement Reaction
    Yuya Inaba, Tomoki Yoneda, Yuichi Kitagawa, Kiyoshi Miyata, Yasuchika Hasegawa, Yasuhide Inokuma
    CHEMICAL COMMUNICATIONS, 56, 3, 348, 351, ROYAL SOC CHEMISTRY, 2020年, ［査読有り］, ［責任著者］
    英語, 研究論文（学術雑誌）, A dodecahexaene analogue cross-conjugated with four carbonyl groups was prepared from an aliphatic tetraketone. Exposure to LED light (>420 nm) led to the splitting of the dodecahexaene conjugation into two hexatriene subunits, connected through a stereogenic carbon atom. The two triene subunits exhibited excitonic coupling in the UV-Vis absorption and CD spectra.
  • Asymmetric Synthesis of a 5,7-Fused Ring System Enabled by an Intramolecular Buchner Reaction with Chiral Rhodium Catalyst
    Takayuki Hoshi, Eisuke Ota, Yasuhide Inokuma, Junichiro Yamaguchi
    Organic Letters, 21, 24, 10081, 10084, 2019年12月20日, ［査読有り］
    研究論文（学術雑誌）, Copyright © 2019 American Chemical Society. A Rh-catalyzed asymmetric intramolecular Buchner ring expansion of α-alkyl-α-diazoesters has been developed. The present protocol generates a 5,7-fused ring system in an enantioselective manner while minimizing β-hydrogen migration, which has been a competing reaction when using α-alkyl-α-diazoesters. The ester functionality at the bridgehead position would be a useful synthetic handle for further derivatization to complex molecules including natural products.
  • Aliphatic Polyketones as Shapable Molecular Chains　　　　　　　　　　　　　　　
    猪熊泰英
    有機合成化学協会誌, 77, 11, 1078, 1085, 2019年11月, ［査読有り］, ［招待有り］
    英語, 研究論文（学術雑誌）
  • Two-Step Transformation of Aliphatic Polyketones into π-Conjugated Polyimines
    Yumehiro Manabe, Mitsuharu Uesaka, Tomoki Yoneda, Yasuhide Inokuma
    The Journal of Organic Chemistry, 84, 16, 9957, 9964, AMER CHEMICAL SOC, 2019年08月, ［査読有り］, ［責任著者］
    英語, 研究論文（学術雑誌）, The chemo- and stereo-selective two-step transformation of aliphatic polyketones composed of 3,3-dimethylpentane-2,4-dione units was achieved to generate pi-conjugated polyimines. Upon treatment with hydrazine, discrete oligoketones with 4-8 carbonyl groups afforded ethylene-bridged oligoisopyrazoles in 80-89% yields. These oligoisopyrazoles underwent stereoselective oxidation at the ethylene bridge to give fully pi-conjugated oligo(isopyrazole-3,5-diyl-trans-vinylene)s in 73-87% yields. Oxidation of the oligoimines drastically changed their absorption and metal-coordination behaviors. Finally, this two-step transformation was applied to polydisperse polymers. Imine formation proceeded almost quantitatively, even for longer polyketones, including docosamer. Subsequent oxidation of the polyimines furnished a virtually insoluble material that showed broad and red-shifted solid-state absorption over the whole visible region resulting from extended pi-conjugation.
  • Control over Coordination Self-Assembly of Flexible, Multidentate Ligands by Stepwise Metal Coordination of Isopyrazole Subunits
    Yoshiko Ashida, Yumehiro Manabe, Shota Yoshioka, Tomoki Yoneda, Yasuhide Inokuma
    Dalton Transactions, 48, 3, 818, 822, ROYAL SOC CHEMISTRY, 2019年01月, ［査読有り］, ［責任著者］
    英語, 研究論文（学術雑誌）, Structurally flexible oligoisopyrazole molecules were self-assembled into discrete complexes with structural diversity upon palladium coordination. Structural convergence was controlled by a stoichiometry change to induce stepwise metal coordination of isopyrazole subunits. Three different types of complexes were selectively generated from a diisopyrazole ligand. Furthermore, tetraisopyrazole ligands were quantitatively assembled into a discrete complex in a predictable manner.
  • Oligoacetylacetones as shapable carbon chains and their transformation to oligoimines for construction of metal-organic architectures
    Uesaka Mitsuharu, Saito Yuki, Yoshioka Shota, Domoto Yuya, Fujita Makoto, Inokuma Yasuhide
    COMMUNICATIONS CHEMISTRY, 1, 1, Springer Science and Business Media LLC, 2018年04月19日, ［査読有り］, ［責任著者］
    研究論文（学術雑誌）, Abstract

    Flexible chain-like molecules can adopt various conformations, but fabrication of complex and higher-order architectures by chain networking or coiling is still a difficult task in organic chemistry. As the degree of freedom increases, the large entropy loss impedes conformation and orientation fixing. Here we report oligo (3,3-dimethylpentane-2,4-dione)s as flexible and shapable carbon chains with many carbonyl groups for chemical modification. Polycarbonylated chains of various lengths are synthesized by terminal-selective silylation and oxidative coupling reactions using silver(I) oxide. We use reactions of 1,3-diketones and 1,4-diketones to reduce the chain length and to induce favourable conformations. When the chains are treated with hydrazine, all the carbonyl groups are converted to imine groups, resulting in the formation of multidentate ligands. Finally, a two-dimensional sheet-like structure and a cylindrical assembly are generated by respectively networking and coiling the carbon chains, with the aid of metal coordination.
  • Bioinspired synthesis of pentalene-based chromophores from an oligoketone chain
    Yuki Saito, Masayuki Higuchi, Shota Yoshioka, Hisanori Senboku, Yasuhide Inokuma
    Chemical Communications, 54, 50, 6788, 6791, Royal Society of Chemistry, 2018年, ［査読有り］, ［責任著者］
    英語, 研究論文（学術雑誌）, We report a bioinspired synthesis of 2,5-dihydropentalene-based chromophores from an aliphatic oligoketone bearing 1,3- and 1,4-diketone subunits. Unlike the natural polyketone sequence, fused five-membered rings were formed via an intramolecular aldol condensation. A subsequent Knoevenagel condensation reaction with malononitrile furnished a multiply cross-conjugated π-system with low-lying LUMO levels. Furthermore, pentalenes obtained from a non-conjugated aliphatic chain exhibited visible absorption and solid-state fluorescence.
  • Chiral Crystalline Sponges for the Absolute Structure Determination of Chiral Guests
    KaKing Yan, Ritesh Dubey, Tatsuhiko Arai, Yasuhide Inokuma, Makoto Fujita
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 139, 33, 11341, 11344, AMER CHEMICAL SOC, 2017年08月, ［査読有り］
    英語, 研究論文（学術雑誌）, Chiral crystalline sponges with preinstalled chiral references were synthesized. On the basis of the known configurations of the chiral references, the absolute structures of guest compounds absorbed in the pores of the crystalline sponges can be reliably determined without crystallization or chemical modification.
  • Structural Elucidation of Trace Amounts of Volatile Compounds Using the Crystalline Sponge Method
    Nicolas Zigon, Takashi Kikuchi, Junko Ariyoshi, Yasuhide Inokuma, Makoto Fujita
    CHEMISTRY-AN ASIAN JOURNAL, 12, 10, 1057, 1061, WILEY-V C H VERLAG GMBH, 2017年05月, ［査読有り］
    英語, 研究論文（学術雑誌）, Volatile organic compounds are widely present as scents and odors in our daily lives and are readily found in a variety of natural extracts. Because these compounds are highly volatile and usually available only in minute quantities, little attention has been paid to X-ray diffraction as a technique for their structure determination. Here, we show that the structures of volatile organic compounds are easily elucidated using minute quantities of the compounds and the crystalline sponge method. The compound vapors can be directly absorbed into the sponge crystals, or alternatively, preparative gas chromatography can be used to separate the desired compound from a natural mixture.
  • Finding a New Crystalline Sponge from a Crystallographic Database
    Yasuhide Inokuma, Kazuki Matsumura, Shota Yoshioka, Makoto Fujita
    CHEMISTRY-AN ASIAN JOURNAL, 12, 2, 208, 211, WILEY-V C H VERLAG GMBH, 2017年01月, ［査読有り］
    英語, 研究論文（学術雑誌）, Empirical searching conditions were adopted to identify suitable candidates from the Cambridge Structural Database (CSD) for crystalline sponge hosts for X-ray crystallographic analysis of incoming guest compounds. After optimization of the solvent and soaking conditions, one of the candidates was used as a crystalline sponge for the structure determination of an aromatic guest.
  • X-ray Structure Analysis of Ozonides by the Crystalline Sponge Method
    Shota Yoshioka, Yasuhide Inokuma, Vincent Duplan, Ritesh Dubey, Makoto Fujita
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 138, 32, 10140, 10142, AMER CHEMICAL SOC, 2016年08月, ［査読有り］
    英語, 研究論文（学術雑誌）, The crystalline sponge method was used for the X-ray structure analysis of ozonide compounds. As this new technique requires only microgram quantities of the samples, structural analysis can be conducted without product isolation, isomer separation, or crystallization and most importantly without any risk of explosion.
  • The crystalline sponge method updated
    Manabu Hoshino, Anupam Khutia, Hongzhu Xing, Yasuhide Inokuma, Makoto Fujita
    IUCRJ, 3, 139, 151, INT UNION CRYSTALLOGRAPHY, 2016年03月, ［査読有り］
    英語, 研究論文（学術雑誌）, Crystalline sponges are porous metal complexes that can absorb and orient common organic molecules in their pores and make them observable by conventional X-ray structure analysis (crystalline sponge method). In this study, all of the steps in the crystalline sponge method, including sponge crystal preparation, pore-solvent exchange, guest soaking, data collection and crystallographic analysis, are carefully examined and thoroughly optimized to provide reliable and meaningful chemical information as chemical crystallography. Major improvements in the method have been made in the guest-soaking and data-collection steps. In the soaking step, obtaining a high site occupancy of the guest is particularly important, and dominant parameters for guest soaking (e.g. temperature, time, concentration, solvents) therefore have to be optimized for every sample compound. When standard conditions do not work, a high-throughput method is useful for efficiently optimizing the soaking conditions. The X-ray experiments are also carefully re-examined. Significant improvement of the guest data quality is achieved by complete data collection at high angle regions. The appropriate disorder treatment of the most flexible ZnI2 portions of the host framework and refinement of the solvents filling the remaining void are also particularly important for obtaining better data quality. A benchmark test for the crystalline sponge method toward an achiral molecule is proposed with a guaiazulene guest, in which the guest structure (with similar to 100% site occupancy) is refined without applying any restraints or constraints. The obtained data quality with R-int = 0.0279 and R-1 = 0.0379 is comparable with that of current conventional crystallographic analysis for small molecules. Another benchmark test for this method toward a chiral molecule is also proposed with a santonin guest. The crystallographic data obtained [R-int = 0.0421, R-1 = 0.0312, Flack (Parsons) = -0.0071 (11)] represents the potential ability of this method for reliable absolute structure determination.
  • A saccharide-based crystalline sponge for hydrophilic guests
    Guo-Hong Ning, Kazuki Matsumura, Yasuhide Inokuma, Makoto Fujita
    CHEMICAL COMMUNICATIONS, 52, 43, 7013, 7015, ROYAL SOC CHEMISTRY, 2016年, ［査読有り］
    英語, 研究論文（学術雑誌）, A coordination network composed of a mannose-based organic ligand and a sodium ion, 'sugar sponge', was synthesized for the crystalline sponge analysis of hydrophilic compounds. Owing to multiple hydrogen-bonding interactions, hydrophilic guests are firmly trapped in the 1-dimensional channel. The sugar sponge was utilized to analyze the structures of flexible alcohol and absolute configurations of chiral epoxides.
  • Structure determination of microbial metabolites by the crystalline sponge method
    Yasuhide Inokuma, Tomoya Ukegawa, Manabu Hoshino, Makoto Fujita
    CHEMICAL SCIENCE, 7, 6, 3910, 3913, ROYAL SOC CHEMISTRY, 2016年, ［査読有り］
    英語, 研究論文（学術雑誌）, The structures of metabolites produced in microgram quantities by enzymatic reductions with baker's yeast were analyzed using the crystalline sponge method. The X-ray data provided reliable structures for trace metabolites including their relative and absolute stereochemistries that are not fully addressed by conventional NMR and LC-MS analyses. Technically, combining two or more chromatographic purification techniques is essential because, unlike abundant synthetic compounds, extracted metabolites contain many low level UV-silent impurities. The crystalline sponge method coupled with HPLC purification (LC-SCD) would thus be a useful method for metabolic analysis and drug discovery.
  • Where is the Oxygen? Structural Analysis of -Humulene Oxidation Products by the Crystalline Sponge Method
    Nicolas Zigon, Manabu Hoshino, Shota Yoshioka, Yasuhide Inokuma, Makoto Fujita
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 54, 31, 9033, 9037, WILEY-V C H VERLAG GMBH, 2015年07月, ［査読有り］
    英語, 研究論文（学術雑誌）, Crystal structures of -humulene, a cyclic sesquiterpene, and its oxidized subproducts, were analyzed by the crystalline sponge method. Regio- and stereochemistry, including absolute configuration when a chiral oxidant was applied, and the stable conformations of all the scaffold-related compounds were successfully determined for samples on a 5-50 mu g scale.
  • Absolute structure determination of compounds with axial and planar chirality using the crystalline sponge method
    Shota Yoshioka, Yasuhide Inokuma, Manabu Hoshino, Takashi Sato, Makoto Fujita
    CHEMICAL SCIENCE, 6, 7, 3765, 3768, ROYAL SOC CHEMISTRY, 2015年, ［査読有り］
    英語, 研究論文（学術雑誌）, The absolute stereochemistry of compounds with axial and planar chirality is successfully determined by the crystalline sponge method without crystallization or derivatization of the compounds. This method is applied to absolute structure determination in the asymmetric synthesis of unique compounds with axial and planar chirality.
  • Networked-Cage Microcrystals for Evaluation of Host Guest Interactions
    Shohei Matsuzaki, Tatsuhiko Arai, Koki Ikemoto, Yasuhide Inokuma, Makoto Fujita
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136, 52, 17899, 17901, AMER CHEMICAL SOC, 2014年12月, ［査読有り］
    英語, 研究論文（学術雑誌）, We have developed a new synthetic protocol for the preparation of a microcrystalline powder (median size: X-50 = 25 mu m) of networked M6L4 cages 1a for the stationary phase of an affinity column on a greater than 50 g scale. Analogously to large single crystals 1b (X-50 approximate to 0.5 mm), microcrystals 1a accommodate guest molecules tetrathiafulvalene (TTF) and fullerene (C-60) at up to 32 and 35 wt %, respectively. Importantly, the hostguest interactions within networked cages could be evaluated in terms of the retention time from HPLC analysis by using microcrystals 1a as the stationary phase. In this way, favorable guests for networked cages 1 and even solution M6L4 cage 2 could easily be assessed by HPLC.
  • Visualization of Solution Chemistry by X-ray Crystallography Using Porous Coordination Networks
    Yasuhide Inokuma, Makoto Fujita
    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 87, 11, 1161, 1176, CHEMICAL SOC JAPAN, 2014年11月, ［査読有り］
    英語, Porous coordination networks have two distinctive characteristics: robust coordination frameworks and fluid pores wherein molecules are mobile. These characteristics allow solution chemistry to be performed in the crystalline state, thus enabling single-crystal X-ray observation of various reactions and host-guest complexation usually observed in solution. From this viewpoint, porous coordination networks can be used as a tool for visualizing solution-based chemical reactions. Using this tool, we have visualized chemical reactions within porous coordination network crystals to elucidate the reaction mechanisms and to determine the molecular structures of the products and intermediates. When the nanospace of porous coordination networks is cleverly designed on the basis of the structures of hollow molecular hosts in solution, solution-like host guest chemistry is also reproduced in crystals, therefore enabling their visualization by X-ray crystallography. Furthermore, a new method based on crystalline-state host-guest chemistry was developed for the single-crystal X-ray analysis of trace amounts of noncrystalline compounds using porous coordination networks. In this account, we review and discuss the visualization of unique solution-like phenomena by single-crystal X-ray analysis using porous coordination networks as crystalline hosts.
  • Radical C-H Functionalization of Heteroarenes under Electrochemical Control
    Alexander G. O'Brien, Akinobu Maruyama, Yasuhide Inokuma, Makoto Fujita, Phil S. Baran, Donna G. Blackmond
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 53, 44, 11868, 11871, WILEY-V C H VERLAG GMBH, 2014年10月, ［査読有り］
    英語, 研究論文（学術雑誌）, Electrochemical reactions are shown to be effective for the C-H functionalization of a number of heterocyclic substrates that are recalcitrant to conventional peroxide radical initiation conditions. Monitoring reaction progress under electrochemical conditions provides mechanistic insight into the C-H functionalization of a series of heterocycles of interest in medicinal chemistry.
  • X-ray Snapshot Observation of Palladium-Mediated Aromatic Bromination in a Porous Complex
    Koki Ikemoto, Yasuhide Inokuma, Kari Rissanen, Makoto Fujita
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136, 19, 6892, 6895, AMER CHEMICAL SOC, 2014年05月, ［査読有り］
    英語, 研究論文（学術雑誌）, Pd-mediated aromatic bromination is intriguing to synthetic and organometallic chemists due to both its synthetic utility and, more importantly, a proposed mechanism involving an uncommon Pd(IV)/Pd(II) catalytic cycle. Here, we report an X-ray snapshot observation of a Pd reaction center during a Pd-mediated aromatic bromination in a single crystal of a porous coordination network crystalline scaffold. Upon treatment of a single crystal with N-bromosuccinimide, sequential X-ray snapshots revealed that the aryl-Pd(II)-L species embedded in the network pores was converted to the brominated aryl product through a transient aryl-Pd(II)-Br species, which is normally unobservable because of its rapid dimerization into insoluble Pd-2(mu-Br)(2) species. Though the reaction pathway may be biased by the crystalline state, the new X-ray snapshot method relies on crystalline flasks to provide important mechanistic insight.
  • Preparation and guest-uptake protocol for a porous complex useful for 'crystal-free' crystallography
    Yasuhide Inokuma, Shota Yoshioka, Junko Ariyoshi, Tatsuhiko Arai, Makoto Fujita
    NATURE PROTOCOLS, 9, 2, 246, 252, NATURE PUBLISHING GROUP, 2014年02月, ［査読有り］
    英語, 研究論文（学術雑誌）, We recently reported a new method for single-crystal X-ray diffraction (SCD) analysis that does not require the crystallization of the target compound. In this 'crystal-free' crystallography, a tiny crystal of a porous complex is soaked in the solution of the target guest. The guest molecules are absorbed and oriented in the crystal pores and can be analyzed by X-ray diffraction. We describe here a detailed synthetic protocol for the preparation of uniform single crystals of the porous host complex and for the subsequent guest uptake. The protocol describes our most versatile porous complex, which is prepared from commercially available ZnI2 and 2,4,6-tri(4-pyridyl)-1,3,5-triazine. The host complex has large pores with a cross-section of 8 x 5 angstrom(2). Single crystals of the complex are grown from layered solutions of the two components. The pores of the as-synthesized complex are filled with nitrobenzene, which is replaced with the inert solvent cyclohexane. This solvent exchange is essential for the rapid and effective inclusion of target compounds. The most crucial and delicate step is the selection of high-quality single crystals from the mixture of crystals of various shapes and sizes. We suggest using the facial indices of the single crystals as a criterion for crystal selection. Single-crystal samples for X-ray analysis can be prepared by immersing the selected crystals in a cyclohexane/dichloromethane solution of target compound. After a very slow evaporation of the solvent, typically over 2 d, the final crystal can be picked and directly subjected to SCD analysis. The protocol can be completed within similar to 16 d.
  • Stable Encapsulation of Acrylate Esters in Networked Molecular Capsules
    Guo-Hong Ning, Yasuhide Inokuma, Makoto Fujita
    CHEMISTRY-AN ASIAN JOURNAL, 9, 2, 466, 468, WILEY-V C H VERLAG GMBH, 2014年02月, ［査読有り］
    英語, 研究論文（学術雑誌）, Reactive acrylate esters were encapsulated in the cavity of networked molecular capsules in a single-crystal-to-single-crystal fashion. Owing to the encapsulation effect, acrylates inside the capsules do not undergo polymerization upon irradiation with UV light or heating, while the guest molecules can be quantitatively extracted by treatment with toluene.
  • Unique ultrafast energy transfer in a series of phenylene-bridged subporphyrin-porphyrin hybrids
    Juwon Oh, Jooyoung Sung, Masaaki Kitano, Yasuhide Inokuma, Atsuhiro Osuka, Dongho Kim
    CHEMICAL COMMUNICATIONS, 50, 72, 10424, 10426, ROYAL SOC CHEMISTRY, 2014年, ［査読有り］
    英語, 研究論文（学術雑誌）, A series of phenylene-bridged subporphyrin-Zn(II) porphyrin (SubP-ZnP) hybrid systems undergo extraordinarily fast excitation energy transfer (EET) processes from the SubP to the ZnP, aided by conjugative electronic elongation of the SubP to the phenylene-bridge.
  • Dynamic Behavior of M6L4 Capsules in Solution and Crystalline States
    Guo-Hong Ning, Yasuhide Inokuma, Makoto Fujita
    CHEMISTRY-AN ASIAN JOURNAL, 8, 11, 2596, 2599, WILEY-V C H VERLAG GMBH, 2013年11月, ［査読有り］
    英語, 研究論文（学術雑誌）
  • X-ray analysis on the nanogram to microgram scale using porous complexes (vol 495, pg 461, 2013)
    Yasuhide Inokuma, Shota Yoshioka, Junko Ariyoshi, Tatsuhiko Arai, Yuki Hitora, Kentaro Takada, Shigeki Matsunaga, Kari Rissanen, Makoto Fujita
    NATURE, 501, 7466, 262, 262, NATURE PUBLISHING GROUP, 2013年09月, ［査読有り］
    英語
  • X-ray analysis on the nanogram to microgram scale using porous complexes
    Yasuhide Inokuma, Shota Yoshioka, Junko Ariyoshi, Tatsuhiko Arai, Yuki Hitora, Kentaro Takada, Shigeki Matsunaga, Kari Rissanen, Makoto Fujita
    NATURE, 495, 7442, 461, +, NATURE PUBLISHING GROUP, 2013年03月, ［査読有り］
    英語, 研究論文（学術雑誌）, X-ray single-crystal diffraction (SCD) analysis has the intrinsic limitation that the target molecules must be obtained as single crystals. Here we report a protocol for SCD analysis that does not require the crystallization of the sample. In our method, tiny crystals of porous complexes are soaked in a solution of the target, such that the complexes can absorb the target molecules. Crystallographic analysis clearly determines the absorbed guest structures along with the host frameworks. Because the SCD analysis is carried out on only one tiny crystal of the complex, the required sample mass is of the nanogram-microgram order. We demonstrate that as little as about 80 nanograms of a sample is enough for the SCD analysis. In combination with high-performance liquid chromatography, our protocol allows the direct characterization of multiple fractions, establishing a prototypical means of liquid chromatography SCD analysis. Furthermore, we unambiguously determined the structure of a scarce marine natural product using only 5 micrograms of the compound.
  • Reagent-Installed Capsule Network: Selective Thiocarbamoylation of Aromatic Amines in Crystals with Preinstalled CH3NCS
    Yasuhide Inokuma, Guo-Hong Ning, Makoto Fujita
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 51, 10, 2379, 2381, WILEY-V C H VERLAG GMBH, 2012年, ［査読有り］
    英語, 研究論文（学術雑誌）
  • Bimolecular Reaction via the Successive Introduction of Two Substrates into the Crystals of Networked Molecular Cages
    Yasuhide Inokuma, Nodoka Kojima, Tatsuhiko Arai, Makoto Fujita
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133, 49, 19691, 19693, AMER CHEMICAL SOC, 2011年12月, ［査読有り］
    英語, 研究論文（学術雑誌）, Two substrates, 4-hydroxydiphenylamine (3) and ethyl isocyanate (4), were successively introduced into the crystals of networked M6L4 cages 1. Because of the encapsulation effect, most of the initially introduced substrate 3 remained within the crystals during immersion in a solution of 4. X-ray analysis revealed that before the reaction, the nucleophilic NH group of 3 is effectively protected by tight packing within the cage units while the OH group is exposed to the incoming second substrate. Successive introduction of 4 into the crystal results in the chemoselective acylation of 3 at the less nucleophilic OH group. The observed chemoselectivity is consistent with that exhibited by discrete M6L4 cage 2 in solution.
  • Diels-Alder via Molecular Recognition in a Crystalline Molecular Flask
    Koki Ikemoto, Yasuhide Inokuma, Makoto Fujita
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133, 42, 16806, 16808, AMER CHEMICAL SOC, 2011年10月, ［査読有り］
    英語, 研究論文（学術雑誌）, In the pore of a porous coordination network, Diels-Alder reactants, a diene and a dienophile, are recognized by donor-acceptor and multiple H-bond interactions, respectively, and fixed at ideal positions for the reaction. Heating the crystals promoted the Diels-Alder reactions with enhanced reactivity and controlled regioselectivity as clearly monitored by in situ X-ray crystallography.
  • Crystalline molecular flasks
    Yasuhide Inokuma, Masaki Kawano, Makoto Fujita
    NATURE CHEMISTRY, 3, 5, 349, 358, NATURE PUBLISHING GROUP, 2011年05月, ［査読有り］
    英語, A variety of host compounds have been used as molecular-scale reaction vessels, protecting guests from their environment or restricting the space available around them, thus favouring particular reactions. Such molecular 'flasks' can endow guest molecules with reactivities that differ from those in bulk solvents. Here, we extend this concept to crystalline molecular flasks, solid-state crystalline networks with pores within which pseudo-solution-state reactions can take place. As the guest molecules can spontaneously align along the walls and channels of the hosts, structural changes in the substrates can be directly observed by in situ X-ray crystallography during reaction. Recently, this has enabled observation of the molecular structures of transient intermediates and other labile species, in the form of sequential structural snapshots of the chemical transformation. Here, we describe the principles, development and applications of crystalline molecular flasks.
  • Synthesis and Properties of Boron(III)-Coordinated Subbacteriochlorins
    Shin-ya Hayashi, Eiji Tsurumaki, Yasuhide Inokuma, Pyosang Kim, Young Mo Sung, Dongho Kim, Atsuhiro Osuka
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133, 12, 4254, 4256, AMER CHEMICAL SOC, 2011年03月, ［査読有り］
    英語, 研究論文（学術雑誌）, Subbacteriochlorins, which were prepared via hydrogenation of subporphyrins with Raney nickel, are modestly aromatic due to 14 pi-diazaannulenic circuit and exhibit characteristic blue-shifted Soret-like bands, intensified fluorescence spectra, and high oxidation potentials.
  • Oxocyclohexadienylidene-Substituted Subporphyrins
    Shin-Ya Hayashi, Jooyoung Sung, Young Mo Sung, Yasuhide Inokuma, Dongho Kim, Atsuhiro Osuka
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 50, 14, 3253, 3256, WILEY-BLACKWELL, 2011年, ［査読有り］
    英語, 研究論文（学術雑誌）
  • Shedding light on hidden reaction pathways in radical polymerization by a porous coordination network
    Yasuhide Inokuma, Satoshi Nishiguchi, Koki Ikemoto, Makoto Fujita
    CHEMICAL COMMUNICATIONS, 47, 44, 12113, 12115, ROYAL SOC CHEMISTRY, 2011年, ［査読有り］
    英語, 研究論文（学術雑誌）, A coordination network comprising 2-vinyltriphenylene was treated with AIBN at a high temperature, but the radical polymerization of the vinyl monomer was completely suppressed by spatial separation and otherwise hidden aerobic oxidation pathways are enhanced.
  • Networked molecular cages as crystalline sponges for fullerenes and other guests
    Yasuhide Inokuma, Tatsuhiko Arai, Makoto Fujita
    NATURE CHEMISTRY, 2, 9, 780, 783, NATURE PUBLISHING GROUP, 2010年09月, ［査読有り］
    英語, 研究論文（学術雑誌）, Many molecular cages selectively bind guests in solution, but in the solid state close packing often prevents guest entry, which renders the cages inactive. We envisioned that coordination networks constructed from well-known molecular cages could transfer the richness of solution-state host-guest chemistry into the solid state. We report a crystalline coordination network generated from an infinite array of octahedral M(6)L(4) cage subunits (M = metal, L = ligand). This coordination network is a 'crystalline molecular sponge' engineered on the molecular level and retains similar guest recognition properties to those found in solution. The network crystallinity is robust and thus X-ray diffraction analysis can be used to unambiguously observe single-crystal to single-crystal guest inclusion. The void spaces define alternating M(12)L(8) and M(12)L(24) cuboctahedral molecular cages and these large cages absorb up to 35 weight per cent of C(60) or C(70) by simply soaking the crystals in a toluene solution of the fullerene. When the crystals are immersed in fullerene mixtures, C(70) is preferentially absorbed.
  • meso-Tris(oligo-2,5-thienylene)-Substituted Subporphyrins
    Shin-ya Hayashi, Yasuhide Inokuma, Atsuhiro Osuka
    ORGANIC LETTERS, 12, 18, 4148, 4151, AMER CHEMICAL SOC, 2010年09月, ［査読有り］
    英語, 研究論文（学術雑誌）, meso-Tris(oligo-2,5-thienylene)-substituted subporphyrins exhibit remarkably red-shifted and intensified absorption bands with increasing number of thienyl subunits. A dimeric subporphyrin obtained from homocoupling of a monobrominated tris(2-thienyl)-substituted subporphyrin exhibits a split Soret-like band due to the exciton coupling.
  • meso-Trifluoromethyl-substituted Subporphyrin from Ring-splitting Reaction of meso-Trifluoromethyl-substituted [32]Heptaphyrin(1.1.1.1.1.1.1)
    Ryu Sakamoto, Shohei Saito, Soji Shimizu, Yasuhide Inokuma, Naoki Aratani, Atsuhiro Osuka
    CHEMISTRY LETTERS, 39, 5, 439, 441, CHEMICAL SOC JAPAN, 2010年05月, ［査読有り］
    英語, 研究論文（学術雑誌）, meso-Trifluoromethyl-substituted subporphyrin was obtained through an extrusion reaction from meso-trifluoromethyl-substituted heptaphyrin(1.1.1.1.1.1.1) upon combined metallation of Cu(II) and B(III) ions. The subporphyrin exhibited the most blue-shifted Soret-like absorption band among those ever prepared.
  • Meso-Trialkyl-Substituted Subporphyrins
    Shin-ya Hayashi, Yasuhide Inokuma, Shanmugam Easwaramoorthi, Kil Suk Kim, Dongho Kim, Atsuhiro Osuka
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 49, 2, 321, 324, WILEY-V C H VERLAG GMBH, 2010年, ［査読有り］
    英語, 研究論文（学術雑誌）
  • A Porous Coordination Network Catalyzes an Olefin Isomerization Reaction in the Pore
    Kazuaki Ohara, Masaki Kawano, Yasuhide Inokuma, Makoto Fujita
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 132, 1, 30, +, AMER CHEMICAL SOC, 2010年01月, ［査読有り］
    英語, 研究論文（学術雑誌）, All-trans retinal efficiently diffused into the pore of a porous coordination network consisting of Znl(2) and an electron-deficient triazine-cored ligand. Enclathrated retinal was isomerized into the 13-cis form and easily replaced with all-trans retinal in solution, thus revealing the catalysis of retinal isomerization by the porous network.
  • Regioselecitive Huisgen Cycloaddition within Porous Coordination Networks
    Takehide Kawamichi, Yasuhide Inokuma, Masaki Kawano, Makoto Fujita
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 49, 13, 2375, 2377, WILEY-V C H VERLAG GMBH, 2010年, ［査読有り］
    英語, 研究論文（学術雑誌）
  • The Catalytic Z to E Isomerization of Stilbenes in a Photosensitizing Porous Coordination Network
    Kazuaki Ohara, Yasuhide Inokuma, Makoto Fujita
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 49, 32, 5507, 5509, WILEY-V C H VERLAG GMBH, 2010年, ［査読有り］
    英語, 研究論文（学術雑誌）
  • The Reaction of Organozinc Compounds with an Aldehyde within a Crystalline Molecular Flask
    Koki Ikemoto, Yasuhide Inokuma, Makoto Fujita
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 49, 33, 5750, 5752, WILEY-V C H VERLAG GMBH, 2010年, ［査読有り］
    英語, 研究論文（学術雑誌）
  • A Molecular Capsule Network: Guest Encapsulation and Control of Diels-Alder Reactivity
    Yasuhide Inokuma, Shota Yoshioka, Makoto Fujita
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 49, 47, 8912, 8914, WILEY-V C H VERLAG GMBH, 2010年, ［査読有り］
    英語, 研究論文（学術雑誌）
  • 1,4-Phenylene-bridged Subporphyrin-Porphyrin Dyad, Triad, and Tetrad
    Yasuhide Inokuma, Shin-ya Hayashi, Atsuhiro Osuka
    CHEMISTRY LETTERS, 38, 3, 206, 207, CHEMICAL SOC JAPAN, 2009年03月, ［査読有り］
    英語, 研究論文（学術雑誌）, 1,4-Phenylene-bridged subporphyrin-porphyrin hybrid molecules were prepared by the Suzuki-Miyaura cross coupling reaction of meso-(4-bromophenyl)-substituted subporphyrin 2 and 5-pinacolateboryl porphyrin 3. In all hybrid models examined, intramolecular energy transfer from the subporphyrin moiety to the porphyrin moieties proceeds efficiently.
  • Peripheral Hexabromination, Hexaphenylation, and Hexaethynylation of meso-Aryl-Substituted Subporphyrins
    Eiji Tsurumaki, Yasuhide Inokuma, Shanmugam Easwaramoorthi, Jong Min Lim, Dongho Kim, Atsuhiro Osuka
    CHEMISTRY-A EUROPEAN JOURNAL, 15, 1, 237, 247, WILEY-BLACKWELL, 2009年, ［査読有り］
    英語, 研究論文（学術雑誌）, Effective peripheral fabrication methods of meso-aryl-substituted subporphyrins were explored for the first time. Hexabrominated subporphyrins 2 were prepared quantitatively from the bromination of subporphyrins 1 with bromine. Hexaphenylated subporphyrins 3 and hexaethynylated subporphyrins 4 and 5 were synthesized by Suzuki-Miyaura coupling and Stille coupling, respectively, in good yields. X-ray crystal structures of 2b, 3b, 4b, and 5a revealed preservation of the bowl-shaped bent Structures with bowl depths similar to that of 1. Hexaethynylated subporphyrins exhibit large two-photon-absorption cross-sections clue to effective delocalization of the conjugated network to the ethynyl substituents.
  • Capped Subporphyrins
    Yasuhide Inokuma, Atsuhiro Osuka
    CHEMISTRY-A EUROPEAN JOURNAL, 15, 28, 6863, 6876, WILEY-V C H VERLAG GMBH, 2009年, ［査読有り］
    英語, 研究論文（学術雑誌）, Capped subporphyrins 12-16 with C(3) molecular symmetry were synthesized from 5,10,15-tri(3-aminophenyl)-substituted subporphyrin 8 and tripodal trialdehydes 2-6 by Lindsey's entropically favored macrocyclization. X-ray diffraction analysis has revealed that the concave surface of the subporphyrin core is selectively capped with a 1,3,5-substituted benzene moiety. Capped subporphyrins 15 and 16, with a five-atom arm and thus large inner cavities, exhibit solvent incorporation behavior in their crystal structures. On the other hand, subporphyrins 12 and 13 exhibit tight structures, in which the cap and subporphyrin core are found much closer with average interplanar separations of 3.56 and 3.15 angstrom, respectively. Variable-temperature (1)H NMR measurements revealed that subporphyrins 12, 13, and 16 undergo spiral interconversions between P and M forms depending on the arm length and the electronic nature of the cap. Of these, subporphyrin 13, with a 1,3,5-tri(alkoxycarbonyl)benzene cap strapped by three-atom arms, exhibits a considerably slow spiral interconversion with a large enthalpy change of Delta H(not equal)= 76.4 kJ mol(-1) and a characteristic red-shift of the Soret-like band and enhancement of the Q(0,0) band. These properties are ascribed to considerable through-space charge-transfer interactions between the electron-deficient cap and the subporphyrin core and the multiple CH-pi interactions.
  • Versatile Photophysical Properties of meso-Aryl-Substituted Subporphyrins: Dipolar and Octupolar Charge-Transfer Interactions
    Shanmugam Easwaramoorthi, Jae-Yoon Shin, Sung Cho, Pyosang Kim, Yasuhide Inokuma, Eiji Tsurumaki, Atsuhiro Osuka, Dongho Kim
    CHEMISTRY-A EUROPEAN JOURNAL, 15, 44, 12005, 12017, WILEY-BLACKWELL, 2009年, ［査読有り］
    英語, 研究論文（学術雑誌）, Donor-acceptor systems based on subporphyrins with nitro and amino substituents at meta and para positions of the meso-phenyl groups were synthesized and their photophysical properties have been systematically investigated. These molecules show two types of charge-transfer interactions, that is, from center to periphery and periphery to center depending on the peripheral substitution, in which the subporphyrin moiety plays a dual role as both donor and acceptor. Based on the solvent-polarity-dependent photophysical properties, we have shown that the fluorescence emission of para isomers originates from the solvatochromic, dipolar, symmetry-broken, and relaxed excited states, whereas the non-solvatochromic fluorescence of meta isomers is of the octupolar type with false symmetry breaking. The restricted meso-(4-aminophenyl) rotation at low temperature prevents the intramolecular charge-transfer (ICT)-forming process. The two-photon absorption (TPA) cross-section values were determined by photoexcitation at 800 nm in nonpolar toluene and polar acetonitrile solvents to see the effect of ICT on the TPA processes. The large enhancement in the TPA cross-section value of approximately 3200 GM (1 GM = 10(-50) cm(4)s photon(-1)) with donor-acceptor substitution has been attributed to the octupolar effect and ICT interactions. A correlation was found between the electron-donating/-withdrawing abilities of the peripheral groups and the TPA cross-section values, that is, p-aminophenyl > m-aminophenyl > nitrophenyl. The increased stability of octupolar ICT interactions in highly polar solvents enhances the TPA cross-section value by a factor of approximately 2 and 4, respectively, for p-amino- and m-nitrophenyl-substituted subporphyrins. On the other hand, the stabilization of the symmetry-broken, dipolar ICT state gives rise to a negligible impact on the TPA processes.
  • 3,3 '- and 4,4 '-Biphenylene-Bridged Subporphyrin Dimers
    Yasuhide Inokuma, Atsuhiro Osuka
    ORGANIC LETTERS, 10, 24, 5561, 5564, AMER CHEMICAL SOC, 2008年12月, ［査読有り］
    英語, 研究論文（学術雑誌）, 3,3'- and 4,4'-biphenylene-bridged subporphyrin dimers were synthesized by means of a Ni-catalyzed homocoupling reaction. Distinctly red-shifted absorption bands and enhanced fluorescence were observed only for the latter, indicating effective through-bond interactions through a 4,4'-biphenylene bridge, which is not possible for porphyrins.
  • Unambiguous identification of Mobius aromaticity for meso-Aryl-substituted [28]hexaphyrins(1.1.1.1.1.1)
    Jeyaraman Sankar, Shigeki Mori, Shohei Saito, Harapriya Rath, Masaaki Suzuki, Yasuhide Inokuma, Hiroshi Shinokubo, Kil Suk Kim, Zin Seok Yoon, Jae-Yoon Shin, Jong Min Lim, Yoichi Matsuzaki, Osamu Matsushita, Atsuya Muranaka, Nagao Kobayashi, Dongho Kim, Atsuhiro Osuka
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 130, 41, 13568, 13579, AMER CHEMICAL SOC, 2008年10月, ［査読有り］
    英語, 研究論文（学術雑誌）, meso-Aryl-substituted [28]hexaphyrins(1.1.1.1.1.1) have been examined by (1)H, (13)C, and (19)F NMR spectroscopies, UV-vis absorption spectroscopy, magnetic circular dichroism spectroscopy, and single-crystal X-ray diffraction analysis. All of these data consistently indicate that [28]hexaphyrins(1.1.1.1.1.1) in solution at 25 degrees C exist largely as an equilibrium among several rapidly interconverting twisted Mobius conformations with distinct aromaticities, with a small contribution from a planar rectangular conformation with antiaromatic character at slightly higher energy. In the solid state, [28]hexaphyrins(1.1.1.1.1.1) take either planar or Mobius-twisted conformations, depending upon the meso-aryl substituents and crystallization conditions, indicating a small energy difference between the two conformers. Importantly, when the temperature is decreased to -100 degrees C in THF, these rapid interconversions among Mobius conformations are frozen, allowing the detection of a single [28]hexaphyrin(1.1.1.1.1.1) species having a Mobius conformation. Detailed analyses of the solid-state Mobius structures of compounds 2b, 2c, and 2f showed that singly twisted structures are achieved without serious strain and that cyclic pi-conjugation is well-preserved, as needed for exhibiting strong diatropic ring currents. Actually, the harmonic-oscillator model for aromaticity (HOMA) values of these structures are significantly large (0.85, 0.69, and 0.71, respectively), confirming the first demonstration of stable Mobius aromatic systems consisting of free-base expanded porphyrins without the assistance of metal coordination.
  • Meso-(4-(N,N-dialkylamino)phenyl)-substituted subporphyrins: Remarkably perturbed absorption spectra and enhanced fluorescence by intramolecular charge transfer interactions
    Yasuhide Inokuma, Shanmugam Easwaramoorthi, Zin Seok Yoon, Dongho Kim, Atsuhiro Osuka
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 130, 37, 12234, +, AMER CHEMICAL SOC, 2008年09月, ［査読有り］
    英語, 研究論文（学術雑誌）, A series of meso-(4-(N,N-dibenzylamino)phenyl)-substituted subporphyrins was synthesized by means of Buchwald-Hartwig amination protocol. Substitution of the amino group at the 4-position of the meso-phenyl substituent resulted in a remarkable red shift in the absorption spectra and drastic enhancement of fluorescence intensity probably as a consequence of intramolecular CT interaction. These characteristics have been utilized to construct a cation-sensing system by appending a 1-aza-15-crown-5 unit to subporphyrin that displays large spectral changes upon cation binding.
  • Synthesis and characterization of meso-aryl-substituted subchlorins
    Eiji Tsurumaki, Shohei Saito, Kil Suk Kim, Jong Min Lim, Yasuhide Inokuma, Dongho Kim, Atsuhiro Osuka
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 130, 2, 438, +, AMER CHEMICAL SOC, 2008年01月, ［査読有り］
    英語, 研究論文（学術雑誌）, meso-Aryl-substituted subchlorins were obtained as a side product in acid-catalyzed subporphyrin synthesis and were fully characterized. Subchlorins were more efficiently prepared by reduction of subporphyrins with p-losylhydrazide under basic conditions. Structural change from subporphyrin to subchlorin is accompanied by large optical and electrochemical changes that are quite similar to those observed upon change from porphyrin to chlorin. Optical and electrochemical properties of subchlorins are well understood with the framework of Gouterman's four-orbital theory.
  • Subporphyrins: emerging contracted porphyrins with aromatic 14 pi-electronic systems and bowl-shaped structures: rational and unexpected synthetic routes
    Yasuhide Inokuma, Atsuhiro Osuka
    DALTON TRANSACTIONS, 19, 2517, 2526, ROYAL SOC CHEMISTRY, 2008年, ［査読有り］
    英語, 研究論文（学術雑誌）, Subporphyrin is a ring-contracted porphyrin congener consisting of three pyrrolic subunits domed in a C(3) symmetric bowl arrangement. Subporphyrin had long been elusive until the first synthesis of tribenzosubporphine in 2006. Shortly after, synthetic protocols of subpyriporphyrin, meso-aryl-substituted subporphyrins, and meso-aryl substituted subchlorins were developed. Subporphyrins display interesting properties including distinct aromaticity arising from 14 pi-electronic conjugation, green fluorescence, and strong in fluences of meso-aryl substituents on the electronic network of the macrocycle. Besides the rational synthetic routes, an unexpected route to a specific subporphyrin from a [32] heptaphyrin(1.1.1.1.1.1.1) was discovered via a thermal extrusion reaction upon Cu(II)-B(III) cooperative metallation. In this Perspective, we review recent progress on subporphyrin chemistry and unprecedented ring-splitting reactions of medium size expanded porphyrins that are triggered upon metallation.
  • Effective expansion of the subporphyrin chromophore through conjugation with meso-oligo(1,4-phenyleneethynylene) substituents: Octupolar effect on two-photon absorption
    Yasuhide Inokuma, Shanmugam Easwaramoorthi, So Young Jang, Kil Suk Kim, Dongho Kim, Atsuhiro Osuka
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 47, 26, 4840, 4843, WILEY-BLACKWELL, 2008年, ［査読有り］
    英語, 研究論文（学術雑誌）
  • meso-aryl-substituted subporphyrins: Synthesis, structures, and large substituent effects on their electronic properties
    Yasuhide Inokuma, Zin Seok Yoon, Dongho Kim, Atsuhiro Osuka
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 129, 15, 4747, 4761, AMER CHEMICAL SOC, 2007年04月, ［査読有り］
    英語, 研究論文（学術雑誌）, Two synthetic methods of meso-aryl-substituted subporphyrins have been developed by means of the reaction of pyridine-tri-N-pyrrolylborane with a series of aryl aldehydes. One method relies on the condensation under Adler conditions with chloroacetic acid in refluxing 1,2-dichlorobenzene to afford subporphyrins in 1.1-3.2%, and the other is a two-step reaction consisting of the initial treatment of the two substrates with trifluoroacetic acid at 0 degrees C followed by air-oxidation in refluxing 1,2-dichlorobenzene to provide subporphyrins in up to 5.6% yield. H-1 NMR studies indicate that phenyl and sterically unhindered substituents at the meso position of subporphyrins rotate rather freely even at -90 degrees C, whereas the rotation of meso-2,4,6-trimethoxyphenyl substituents is strictly prohibited even at 130 degrees C. The structures of six subporphyins have been revealed by X-ray crystallographic analysis to be all cone-shaped tripyrrolic macrocycles. Dihedral angles of meso-phenyl and sterically unhindered aryl substituents to the subporphyrinic core are rather small (38.3-55.7 degrees) compared to those of porphyrin analogues, whereas those of meso-2,4,6-trimethoxy-substituted subporphyrins are large (68.7-75.7 degrees). These rotational features of the meso-aryl substituents lead to their large influences on the electronic properties of subporphyrins, as seen for 4-nitrophenyl-substituted subporphyrin 14e that exhibits perturbed absorption and fluorescence spectra, depending upon solvents. Large solvent-polarity dependence of the fluorescence of 14e suggests the charge-transfer character for its excited state. Electrochemical and theoretical studies are performed to understand the electronic properties. Overall, meso-aryl-substituted subporphyrins are promising chromophores in future functional devices.
  • Complementary face-to-face dimer formation from meso-aryl subporphyrins bearing a 2-carboxyphenyl group
    Yasuhide Inokuma, Atsuhiro Osuka
    CHEMICAL COMMUNICATIONS, 28, 2938, 2940, ROYAL SOC CHEMISTRY, 2007年, ［査読有り］
    英語, 研究論文（学術雑誌）, meso-Aryl-substituted subporphyrins bearing a 2-carboxyphenyl group were prepared and shown to form complementary face-to-face dimers upon azeotropic removal of methanol.
  • Tribenzosubporphines: Synthesis and characterization
    Y Inokuma, JH Kwon, TK Ahn, MC Yoo, D Kim, A Osuka
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 45, 6, 961, 964, WILEY-V C H VERLAG GMBH, 2006年, ［査読有り］
    英語, 研究論文（学術雑誌）
  • Enlarged pi-electronic network of a meso-meso, beta-beta, beta-beta triply linked dibenzoporphyrin dimer that exhibits a large two-photon absorption cross section
    Y Inokuma, N Ono, H Uno, DY Kim, SB Noh, D Kim, A Osuka
    CHEMICAL COMMUNICATIONS, 30, 3782, 3784, ROYAL SOC CHEMISTRY, 2005年, ［査読有り］
    英語, 研究論文（学術雑誌）, Enlargement of the pi-electronic network of meso-meso, beta-beta, beta-beta triply linked diporphyrin has been exploited by preparing a corresponding dibenzo-fused porphyrin dimer that exhibits a perturbed absorption spectrum and a large two-photon absorption cross section.
  • A doubly N-fused benzohexaphyrin and its rearrangement to a fluorescent macrocycle upon DDQ oxidation
    Y Inokuma, T Matsunari, N Ono, H Uno, A Osuka
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 44, 12, 1856, 1860, WILEY-V C H VERLAG GMBH, 2005年, ［査読有り］
    英語, 研究論文（学術雑誌）
  • meso-porphyrinyl-substituted porphyrin and expanded porphyrins
    Y Inokuma, A Osuka
    ORGANIC LETTERS, 6, 21, 3663, 3666, AMER CHEMICAL SOC, 2004年10月, ［査読有り］
    英語, 研究論文（学術雑誌）, A series of meso-porphyrinyl-substituted expanded porphyrins were prepared from the 1:1 acid-catalyzed condensation reaction of 4-porphyrinyl-2,3,5,6-tetrafluorobenzaldehyde and pyrrole.

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    猪熊 泰英
    １年目に発見した高い張力を内在した大環状化合物であるCalix[3]pyrroleについての研究を引き続き行い、1,4-ジケトン部位のピロール環形成による鎖長短縮反応による合成および、環構造にかかった高い張力に由来して容易に酸開裂反応を起こすことまでをまとめ、トップジャーナルであるJ. Am. Chem. Soc. 誌に報告した。
    さらに、同様の鎖長短縮反応を用いてpyrroleとfuranの双方を含んだCalix[3]heteroarene類の合成も行い、これらの反応性から環状化合物の張力が評価できることを明らかにした。Calix[3]pyrrole, Calix[1]furan[2]pyrrole, Calix[2]furan[1]pyrroleの順に結晶構造における環歪みが共に大きくなっており、この歪みの大きさと同じ順で酸開裂の速度が速くなることを明らかにした。これによってC―C結合にかかる張力の大きさとC－C結合開裂反応の速度との相関関係を体系的にまとめ上げている。張力を駆動力とした開裂反応にでは、十分に高い反応性を保ったままの鎖状活性中間体が得られる。これを３つのヘテロ芳香環ユニットを持つビルディングユニットとして取り扱うことで、Calix[6]heterole類への変換も達成した。これまでのカリックスピロール合成では、エントロピー的に有利な生成物を化学平衡を通して得ることが主流であったが、この歪み誘起環拡大反応では、歪みエネルギー（エンタルピー）を使ってエントロピー的に不利な巨大環状化合物が合成できることが新しい。
    今後さらなる張力を利用する本反応の適用範囲の拡張、および張力に由来する反応性の関係性の定量的な評価を目指す。
    日本学術振興会, 挑戦的研究(萌芽), 北海道大学, 20K21214
  • ｢中分子ひも｣を鍵とする巨大機能性分子の創成
    創発的研究支援事業
    2022年04月
    国立研究開発法人 科学技術振興機構, 北海道大学, PJ2522A005
  • 脂肪族カルボニル化合物を基盤とする巨大π共役系化合物の「一筆書き合成法」の開発　　　　　　　　　　　　　　　
    若手継続グラント
    2019年04月 - 2022年03月
    猪熊泰英
    公益財団法人 旭硝子財団, 研究代表者, 競争的資金
  • 単結晶構造解析で切り拓くメゾスコピック領域の構造有機化学 研究課題
    若手研究(A)
    2017年04月 - 2021年03月
    猪熊泰英
    単分散の脂肪族ポリケトンを基盤として、柔軟な化合物の構造と機能の相関を明確にしながら、発光性材料や金属-有機構造体など様々な有機機能性材料を開発することに成功した。合成面では最大で炭素鎖が100にもおよぶ単分散ポリケトンの単離にも成功した。さらに、X線回折を使ってポリマーと小分子の固相配列における境界線が比較的小さなオリゴマー領域にあることも見いだした。ポリケトンは構造柔軟性と変換反応の多様性を合わせ持つ化合物群として、構造有機化学および材料開発の分野に新しい研究ターゲットをもたらしたと言える。
    日本学術振興会, 若手研究(A), 北海道大学, 研究代表者, 競争的資金, 17H04872
  • 脂肪族ポリイミン配位子によるアシンメトリック分子認識空間の構築 公募研究　　　　　　　　　　　　　　　
    新学術領域研究(研究領域提案型)
    2017年04月 - 2019年03月
    猪熊泰英
    日本学術振興会, 研究代表者, 競争的資金
  • 重合反応のナノ空間精密制御による構造一義的なポリカルボニル化合物の合成手法開発　　　　　　　　　　　　　　　
    研究奨励
    2016年04月 - 2018年03月
    猪熊泰英
    公益財団法人 旭硝子財団, 研究代表者, 競争的資金
  • 細孔性結晶を用いた微量薬物の分解・代謝過程の可視化　　　　　　　　　　　　　　　
    さきがけ
    2013年10月 - 2017年03月
    猪熊泰英
    国立研究開発法人 科学技術振興機構, 研究代表者, 競争的資金
  • 自己組織化による単結晶性空間の構築と擬溶液反応
    科学研究費助成事業
    2012年 - 2017年
    藤田 誠, 佐藤 宗太, 村瀬 隆史, 猪熊 泰英, 澤田 知久, 藤田 大士
    本研究では、中空錯体のもつナノ空間を通して溶液化学と固相、特に結晶相での化学を統合する事を目的とした。これまで独立に発展してきた２つの化学を統合することで、両者のメリットを活かした新しい化学を確立した。溶液化学に対して単結晶Ｘ線構造解析による分析を可能にすることで、溶液化学における反応や包接現象の機構の可視化に成功した。さらに、その知見を溶液化学へフィードバックさせることで溶液系反応におけるトポケミカル制御を達成した。
    日本学術振興会, 特別推進研究, 東京大学, 24000009
  • ネットワーク化分子カプセルを用いた新しい有機合成手法の開発　　　　　　　　　　　　　　　
    倉田奨励金
    2012年04月 - 2014年03月
    猪熊泰英
    日立財団, 研究代表者, 競争的資金
  • 単結晶内ホストーゲスト化学を基盤とした機能性結晶マテリアルの開発 研究課題
    若手研究(B)
    2011年04月 - 2013年03月
    猪熊泰英
    細孔性結晶を結晶ホストとして用い、その中でホストーゲスト化学を駆使することで、極小量の化合物を結晶化せずにX線結晶構造解析する手法「結晶スポンジ法」を開発するに至った。この手法は、様々な天然物サンプルの構造解析に有効であることを実証した。
    日本学術振興会, 若手研究(B), 東京大学, 研究代表者, 競争的資金, 23750146
  • 細孔性ネットワーク錯体をフラスコに用いた新規有機化学反応の開発と単結晶の機能化 研究課題
    研究活動スタート支援
    2009年 - 2011年03月
    猪熊泰英
    細孔性錯体結晶内で様々な有機化学反応を起こし、その過程をX線結晶構造解析によって詳細に観察できた。また、本研究において溶液中と同じ分子認識能を持った分子ケージネットワークの合成に成功し、固相での高度なホスト-ゲスト化学を展開する足がかりを得た。この成果はさらに発展性があるものと期待される。
    日本学術振興会, 研究活動スタート支援, 東京大学, 研究代表者, 競争的資金, 21850008
  • ボウル型ポルフィリン誘導体の開拓-サブポルフィリン・バッキーポルフィリン合成-
    科学研究費助成事業
    2006年 - 2008年
    猪熊 泰英
    サブポルフィリンの化学修飾を行うことで大幅な分光学的物性の制御に成功し応用に向けた機能発現を達成した。サブポルフィリンの大きなメゾ置換基効果を活かし、メゾ位に1,4-phenyleneethynylene鎖を導入することで吸光係数の増大と蛍光量子収率の倍増に成功した。さらに、メゾ位でのπ共役系の拡張が2光子吸収断面積を大きく増大させることも見出し、非線形光学材料としての有用性も示した。サブポルフィリンの分光学特性を簡便かつ最も大きく変化させる方法として、4-aminophenyl基をメゾ位に導入し分子内電荷移動相互作用を引き起こすという手法を発見した。サブポルフィリンの蛍光はアミノ基が1つ導入されるだけで緑色の13%から赤色の60%にまで長波長シフトを伴って量子収率が増大した。また、吸収スペクトルも可視領域に多大な変化をもたらした。このような性質をさらに応用することで、アザクラウンを持つサブポルフィリンが可視領域でのイオンセンサーになることも見出した。一方、サブポルフィリンに特有なお椀型構造をもとにした化学修飾も行った。3-aminophenyl基をメゾ位に持つサブポルフィリンに様々な長さのリンカーを持つトリアルデヒドを反応させ、キャップトサブポルフィリンというカゴ型分子の高収率合成に成功した。このカゴ型のサブポルフィリンは空間的なπ-π相互作用や螺旋反転の速度変化など、キャップの構造とリンカーの長さに応じて様々な機能を発現することを見出した。これらの性質は、完全にサブポルフィリンオリジナルなものであり、本年度の研究はサブポルフィリンの化学をこれまで以上に深めることができたと言える。
    日本学術振興会, 特別研究員奨励費, 京都大学, 06J03230

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