研究者データベース
| 新井 則義(アライ ノリヨシ) |
| 工学研究院 応用化学部門 有機工業化学分野 |
| 准教授 |
Last Updated :2024/05/09
基本情報
所属
職名
学位
連絡先
- n-arai
eng.hokudai.ac.jp
ホームページURL
J-Global ID
研究分野
担当教育組織
職歴
- 2006年04月 - 現在 北海道大学大学院工学研究院 応用化学部門 准教授
- 2005年04月 - 2006年03月 名古屋産業科学研究所中部TLO 博士研究員
- 2000年04月 - 2005年03月 科学技術振興機構戦略的基礎研究推進事業 分子複合系の構築と機能 博士研究員
- 1998年03月 - 2000年03月 日立化成工業株式会社総合研究所
- 1997年04月 - 1998年03月 東京大学 大学院・理学系研究科 助手
学歴
- 1993年04月 - 1996年03月 東京大学大学院 理学系研究科 化学専攻博士課程
- 1991年04月 - 1993年03月 東京大学大学院 理学系研究科 化学専攻修士課程
- 1989年04月 - 1991年03月 東京大学 理学部 化学科
- 1987年04月 - 1989年03月 東京大学 教養学部 理科Ｉ類
所属学協会
研究活動情報
論文
- Taiga Yurino, Ryo Nishihara, Toshihisa Yasuda, Shuangli Yang, Noriyuki Utsumi, Takeaki Katayama, Noriyoshi Arai, Takeshi OhkumaOrganic Letters 2024年01月11日
- Hiroki Ishikawa, Taiga Yurino, Ryo Komatsu, Ming-Yuan Gao, Noriyoshi Arai, Taichiro Touge, Kazuhiko Matsumura, Takeshi OhkumaOrganic Letters 2023年03月24日
- Noriyoshi Arai, Takeshi OhkumaTetrahedron Letters 88 153588 - 153588 2022年01月 [査読有り][通常論文]
- Noriyoshi Arai, Takeshi OhkumaAsymmetric Hydrogenation and Transfer Hydrogenation 55 - 85 2021年04月26日 [査読有り][招待有り]
- Photosensitized Intramolecular [2+2] Cycloaddition of 1H-Pyrrolo[2,3-b]pyridines Enabled by the Assistance of Lewis AcidsNoriyoshi Arai, Takeshi OhkumaThe Journal of Organic Chemistry 85 23 15717 - 15725 2020年11月 [査読有り][通常論文]
- Noriyoshi Arai, Yuki Okabe, Takeshi OhkumaAdvanced Synthesis & Catalysis 361 24 5540 - 5547 2019年12月17日 [査読有り][通常論文]
- Noriyoshi Arai, Takeshi OhkumaTetrahedron Letters 60 46 151252 - 151252 2019年11月 [査読有り][通常論文]
- Noriyoshi Arai, Takeshi OhkumaOrganic Letters 21 5 1506 - 1510 2019年03月 [査読有り][通常論文]
- Arai, Noriyoshi, Namba, Takanori, Kawaguchi, Kei, Matsumoto, Yuki, Ohkuma, TakeshiAngewandte Chemie, International Edition 57 5 1386 - 1389 2018年01月26日 [査読有り][通常論文]
The asymmetric hydrogenation of aromatic γ- and δ-keto esters into optically active hydroxy esters or diols under the catalysis of a novel DIPSkewphos/3-AMIQ–RuII complex was studied. Under the optimized conditions (8 atm H2, Ru complex/t-C4H9OK=1:3.5, 25 °C) the γ- and δ-hydroxy esters (including γ-lactones) were obtained quantitatively with 97–99 % ee. When the reaction was conducted under somewhat harsh conditions (20 atm H2, [t-C4H9OK]=50 mm, 40 °C), the 1,4- and 1,5-diols were obtained predominantly with 95–99 % ee. The reactivity of the ester group was notably dependent on the length of the carbon spacer between the two carbonyl moieties of the substrate. The reaction of β- and ϵ-keto esters selectively afforded the hydroxy esters regardless of the reaction conditions. This catalyst system was applied to the enantioselective and regioselective (for one of the two ester groups) hydrogenation of a γ-ϵ-diketo diester into a trihydroxy ester. - Arai, Noriyoshi, Ohkuma, TakeshiHeterocycles 96 6 997 - 1035 2018年 [査読有り][招待有り]
- Utsumi, Noriyuki, Arai, Noriyoshi, Kawaguchi, Kei, Katayama, Takeaki, Yasuda, Toshihisa, Murata, Kunihiko, Ohkuma, TakeshiChemCatChem 10 18 3955 - 3959 2018年 [査読有り][通常論文]
- Arai, Noriyoshi, Ohkuma, TakeshiJournal of Organic Chemistry 82 14 7628 - 7636 2017年07月 [査読有り][通常論文]
Aza-Diels Alder-type cycloaddition reactions between a range of N-arylimines and functionalized alkenes were effectively catalyzed by the Cr(III)/bipyridine complex under irradiation of blue light, to give the corresponding 1,2,3,4tetrahydroquinoline derivatives in high yields with excellent diastereoselectivity. Typically, the reaction of benzylideneaniline with 1-vinyl-2-pyrrolidinone proceeded smoothly with a substrate-to catalyst molar ratio (S/C) of 1000 and completed within 4 h at room temperature (20-25 degrees C), affording the cycloaddition product in 97% yield. - Arai, Noriyoshi, Satoh, Hironori, Komatsu, Ryo, Ohkuma, TakeshiChemistry - A European Journal 23 37 8806 - 8809 2017年07月 [査読有り][通常論文]
Double asymmetric hydrogenation of linear beta,beta-disubstituted alpha,beta-unsaturated ketones catalyzed by the DM-SEGPHOS/DMAPEN/Ru-II complex with t-C4H9OK afforded the gamma-substituted secondary alcohols in high diastereo-and enantioselectivities. Some mechanistic experiments suggested that two different reactive species, type (I) and (II), were reversibly formed in this catalytic system: Type (I) with the diamine ligand DMAPEN enantioselectively hydrogenated the enones into the chiral allylic alcohols, and type (II) without the diamine ligand diastereoselectively hydrogenated the allylic alcohols into the gamma-substituted secondary alcohols. This dual catalysis protocol was successfully applied to the reaction of a variety of aliphatic-and aromatic-substituted enone substrates. - Takeshi Ohkuma, Noriyoshi AraiCHEMICAL RECORD 16 6 2801 - 2819 2016年12月 [査読有り][通常論文]
Catalytic asymmetric hydrogenation of ketones through the "metal-ligand cooperative mechanism" has been improved in terms of the efficiency, stereoselectivity, and scope of substrates by varying the arrangement of the catalyst structure and reaction conditions. Imino compounds are also smoothly converted to the optically active amines with appropriate catalysts. This type of catalyst exhibits excellent performance on the asymmetric isomerization of primary allylic alcohols into the optically active aldehydes. This personal account describes recent progress on these topics. - Arai, Noriyoshi, Onodera, Nozomi, Ohkuma, TakeshiTetrahedron Letters 57 37 4183 - 4186 2016年09月 [査読有り][通常論文]
Catalytic chemoselective hydrogenation of organic azides using palladium nanoparticles stabilized by alkyne derivatives was studied. A broad range of aromatic and aliphatic azides were smoothly reduced to the corresponding amines in excellent yields with a quite small amount of the catalyst. Hydrogenation of 3-phenylpropylazide gave 3-phenylpropylamine almost quantitatively with a substrate-to-palladium molar ratio (S/Pd) of 12,900 under 8 atm of H-2. The reaction under 1 atm of H2 also proceeded smoothly with an S/Pd of 1000. Several reduction-sensitive functional groups, such as carbonyl, halide, benzylic OH, and aliphatic nitro were well tolerated under the reaction conditions. (C) 2016 Elsevier Ltd. All rights reserved. - 新井則義, 大熊毅有機合成化学協会誌 74 4 360 - 371 2016年04月 [査読有り][招待有り]
Novel methods for the construction of molecular frameworks were developed by means of photochemical activation of 5-membered heteroaromatics, including furans, thiophenes, thiazoles, and oxazoles. Intramolecular Diels-Alder-type cycloaddition reactions between furan and an unactivated alkene moiety were found to proceed in high yields in the presence of 9,10-dicyanoanthracene under UV irradiation to afford oxabicyclo[2.2.1]heptane derivatives with high stereoselectivity. Photoirradiation onto alpha-arylthiophene derivatives linked with an alkene moiety through a three-atom spacer gave unprecedented cyclobutene-fused perhydrothiapentalene-type compounds in high yields with high stereoselectivity. A photo-ene type cyclization of 2-aryloxazole derivatives linked with an alkene moiety through a three-atom spacer at the 5-position gave a range of functionalized spiro[4.4] cyclic compounds that included cyclopentane, tetrahydrofuran, and pyrrolidine moieties in moderate to high yields with excellent diastereoselectivity. - Noriyoshi Arai, Nozomi Onodera, Atsushi Dekita, Junichi Hori, Takeshi OhkumaTETRAHEDRON LETTERS 56 25 3913 - 3915 2015年06月 [査読有り][通常論文]
Palladium nanoparticles stabilized by alkyne derivatives catalyzed the hydrogenation of nitroarenes to the aryl amines in homogeneous phase. The reaction of nitrobenzene proceeded smoothly with a substrate-to-palladium molar ratio (S/Pd) of 51,000 under 8 atm of H-2. The reaction under 1 atm of H-2 with an S/Pd of 1030 was completed in 4 h. A series of substituted nitroarenes, including 4-acetyl- and 4-formylnitrobenzenes, were converted to the aryl amines with high chemoselectivity. (C) 2015 Elsevier Ltd. All rights reserved. - Novel intramolecular cyclization-skeletal reorganization of 2-arylthiazoles under photoirradiationArai, Noriyoshi, Mizota, Moe, Ohkuma, TakeshiHeterocycles 90 1 607 - 616 2015年01月 [査読有り][通常論文]
Photoirradiation of 2-arylthiazoles derivatives linked with an alkene moiety through a three-atom spacer was investigated. The main products were unexpected tetrahydrofuran-fused thiazepine derivatives with concomitant formation of [2+2] cycloaddition products and regioisomeric thiazoles. The product distribution was little influenced by the reaction conditions and substituents of the substrates. - Noriyoshi Arai, Moe Mizota, Takeshi OhkumaORGANIC LETTERS 17 1 86 - 89 2015年01月 [査読有り][通常論文]
A novel photocyclization of 2-aryloxazole derivatives linked with an alkene moiety through a three-atom spacer at the 5-position gave a range of functionalized spiro[4.4] cyclic compounds that included cyclopentane, tetrahydrofuran, and pyrrolidine moieties in moderate to high yields with excellent diastereoselectivity. - Arai, Noriyoshi, Sato, Keisuke, Azuma, Keita, Ohkuma, TakeshiAngewandte Chemie, International Edition 52 29 7500 - 7504 2013年07月 [査読有り][通常論文]
- Arai, Noriyoshi, Satoh, Hironori, Utsumi, Noriyuki, Murata, Kunihiko, Tsutsumi, Kunihiko, Ohkuma, TakeshiOrganic Letters 15 12 3030 - 3033 2013年06月 [査読有り][通常論文]
Enantioselective hydrogenation of alkynyl ketones catalyzed by Ru(OTf)(TsDPEN)(eta(6)-p-cymene) (TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) affords the propargylic alcohols in up to 97% ee. The alkynyl moieties are left intact In most cases. The reaction can be conducted with a substrate-to-catalyst molar ratio as high as 5000 under 10 atm of H-2. The mode of enantioselection is elucidated with the transition state models directed by the CH/pi attractive interaction between the substrate and the catalytic species. - Noriyoshi Arai, Yu Saruwatari, Kotaro Isobe, Takeshi OhkumaAdvanced Synthesis and Catalysis 355 14-15 2769 - 2774 2013年 [査読有り][通常論文]
The ruthenabicyclic complex RuCl[(R)-daipena][(R)-dm-segphos] with potassium tert-butoxide catalyzes the hydrogenation of 2-alkylquinoxalines and a 3-methyl-2H-1,4-benzoxazine in toluene under 20-100 atm of hydrogen at 40 °C to afford S-configured cyclic amino products in greater than 97% enantiomeric excess {DAIPENA=anion of DAIPEN at the 2-position of an anisyl group, DAIPEN=1,1-di (4-anisyl)-2-isopropyl-1,2-ethylenediamine, DM-SEGPHOS=(4,4′-bi-1,3-benzodioxole)-5,5′-diylbis[di(3,5-xylyl) phosphine]}. The high catalytic activity results in a turnover number as high as 9400. Hydrogenation of the benzoimine heterocycles with the RuCl[(R)-daipena][(R)-segphos]/ potassium tert-butoxide system yields the R-configured products in high enantiomeric excess [SEGPHOS=(4,4′-bi-1,3- benzodioxole)-5,5′-diylbis-(diphenylphosphine)]. The mode of enantioselection is discussed based on transition state models involving six-membered pericyclic structures. © 2013 Wiley-VCH Verlag GmbH& Co. KGaA, Weinheim. - T. Ohkuma, N. AraiComprehensive Chirality 5 270 - 300 2012年09月 [査読有り][通常論文]
In this chapter asymmetric hydrogenation of ketones by the use of chiral catalysts is described. In the first part, the asymmetric hydrogenation of functionalized ketones including β-keto esters, α-keto esters, and α-alkoxy or amino ketones is discussed mainly in homogeneous catalytic systems. In the second part, we describe the highly stereoselective manner of the reaction with nonfunctionalized (simple) ketones. The final part of this chapter deals with the highly diastereo- and enantioselective hydrogenation accompanied by dynamic kinetic resolution. © 2012 Elsevier Ltd. All rights reserved. - Noriyoshi Arai, Noriyuki Utsumi, Yuki Matsumoto, Kunihiko Murata, Kunihiko Tsutsumi, Takeshi OhkumaADVANCED SYNTHESIS & CATALYSIS 354 11-12 2089 - 2095 2012年08月 [査読有り][通常論文]
The new catalyst system of RuBr2[(S,S)-xyl-skewphos][(S,S)-dpen] and potassium tert-butoxide shows high reactivity and enantioselectivity in the hydrogenation of N-arylimines [Xyl-Skewphos=2,4-bis(di-3,5-xylylphosphino)pentane, DPEN=1,2-diphenylethylenediamine]. A range of imines derived from aromatic and heteroaromatic ketones as well as some ferrocenyl and vinylic imines are hydrogenated with a turnover number as high as 18,000 under 10-50 atm of hydrogen to afford the amine products in up to 99% enantiomeric excess. The reaction is applied to the synthesis of a chiral N-arylamine, which is the synthetic intermediate of a biologically active compound. The mode of enantioselection is interpreted by using transition-state models based on the X-ray structure of the Xyl-Skewphos/DPEN-RuBr2 complex. - Noriyoshi Arai, Takeshi OhkumaCHEMICAL RECORD 12 2 284 - 289 2012年04月 [査読有り][招待有り]
Development of highly active catalysts has been an important research area in synthetic chemistry, especially from a practical point of view. Herein, we focus on the homogeneous catalytic hydrogenation using well-defined molecular catalysts and discuss recent advances in the field with regard to the turnover number for these catalysts. DOI 10.1002/tcr.201100019 - Noriyoshi Arai, Koichiro Tanaka, Takeshi OhkumaORGANIC LETTERS 14 6 1488 - 1491 2012年03月 [査読有り][通常論文]
Photoirradiation of alpha-arylthiophene derivatives linked with an alkene moiety through a three-atom spacer gave unprecedented cyclobutene-fused perhydrothiapentalene-type compounds in high yields, but neither [2 + 2] nor [4 + 2] cycloaddition products. The reaction afforded a single diastereomer in many cases. The chemical structure and relative configuration of a typical product were unambiguously determined by X-ray crystallographic analysis. - Masaya Akashi, Noriyoshi Arai, Tsutomu Inoue, Takeshi OhkumaADVANCED SYNTHESIS & CATALYSIS 353 11-12 1955 - 1960 2011年08月 [査読有り][通常論文]
alpha-Substituted chiral ketones that have small steric and electronic differences around the reaction sites are difficult substrates to reduce with high diastereoselectivity. Metal hydride reduction of 2-(4-benzoylmorpholinyl) phenyl ketone and 3-(1-tert-butoxycarbonylpiperidinyl) phenyl ketone using sodium borohydride, zinc borohydride, and potassium tri-sec-butylborohydride as reducing agents affords the syn- and anti-alcohols in a lower than 80:20 ratio. Hydrogenation of these ketones with a catalyst system of RuCl(2)(BIPHEP) (DMEN) and potassium tert-butoxide in 2-propanol results in the syn-alcohols with >= 99:1 selectivity [BIPHEP= 2,2'-bis(diphenylphosphino)biphenyl, DMEN= N,N-dimethylethylenediamine]. The marked difference in the diastereoselectivity suggests that the stereoselection in this hydrogenation is primarily regulated by the structure of the catalyst's reaction field ("catalyst-controlled diastereoselection") but not the internal stereocontrol of the substrates. This chemistry is applied to the asymmetric hydrogenation through dynamic kinetic resolution with a RuCl(2)[(S)-BINAP][(R)-DMAPEN]/potassium tert-butoxide catalyst [BINAP= 2,2'-bis(diphenylphosphino)- 1,1'-binaphthyl, DMAPEN = 2-dimethylamino-1-phenylethylamine]. A series of aryl heterocycloalkyl ketones has been converted to the alcohols in excellent diastereo- and enantioselectivities. The modes of catalyst-controlled diastereoselection and enantioselection are interpreted by using transition-state molecular models. (S,S)-Reboxetine, a selective norepinephrine uptake inhibitor, was synthesized from one of product alcohols. - Kazuhiko Matsumura, Noriyoshi Arai, Kiyoto Hori, Takao Saito, Noboru Sayo, Takeshi OhkumaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 133 28 10696 - 10699 2011年07月 [査読有り][通常論文]
A novel ruthenabicyclic complex with base shows excellent catalytic activity in the asymmetric hydrogenation of ketones. The turnover frequency of the hydrogenation of acetophenone reaches about 35 000 min(-1) in the best case, affording 1-phenylethanol in >99% ee. Several aliphatic and base-labile ketones are smoothly converted to the corresponding alcohols in high enantioselectivity. The catalytic cycle for this hydrogenation, in which the ruthenabicyclic structure of the catalyst is maintained, is proposed on the basis of the deuteration experiment and spectroscopic analysis data. - Noriyoshi Arai, Takeshi OhkumaTETRAHEDRON 67 9 1617 - 1622 2011年03月 [査読有り][通常論文]
Reaction of O-propargyl salicylaldehyde and related compounds with dialkylamines in the presence of copper(I) iodide gave 4-(alkylamino)-3-methylenechroman derivatives in good yields through the loss of one alkyl group of the dialkylamine. The reaction also worked well by employing 2-amino benzaldehyde derivatives to afford 4-(alkylamino)-3-methylene-1,2,3,4-tetrahydroquinolines. A deuterium-labeling experiment suggested that the a-hydrogen of the dialkylamine was transferred intramolecularly into the terminal methylene. This result indicated the reaction mechanism, which involved the formation of iminium ion between the aldehyde and the dialkylamine followed by ene-type C-C bond formation with inverse electron demand and hydrolysis. (C) 2011 Elsevier Ltd. All rights reserved. - Noriyoshi Arai, Masaya Akashi, Satoshi Sugizaki, Hirohito Ooka, Tsutomu Inoue, Takeshi OhkumaORGANIC LETTERS 12 15 3380 - 3383 2010年08月 [査読有り][通常論文]
Hydrogenation of 3-quinuclidinone and bicyclo[2.2.2]octan-2-one with a combined catalyst system of RuCl(2)[(S)-binap][(R)-iphan] and t-C(4)H(9)OK in 2-propanol afforded the chiral alcohols in 97-98% ee. 2-Diphenylmethyl-3-quinuclidinone was hydrogenated with the same catalyst to the cis alcohol with perfect diastereo- and enantioselectivity. The reaction of unsymmetrical ketones with a bicyclo[2.2.1] or -[2.2.2] skeleton gave the corresponding alcohols with high stereoselectivity. - Noriyoshi Arai, Koichiro Tanaka, Takeshi OhkumaTETRAHEDRON LETTERS 51 9 1273 - 1275 2010年03月 [査読有り][通常論文]
A photosensitized reaction of furan with a non-activated simple alkene was investigated Intramolecular Diels-Alder-type cycloaddition reactions between furan and a trisubstituted alkene were found 10 proceed in high yield in the presence of 9,10-dicyanoanthracene under UV irradiation to afford oxabicyclo[2 2 1]heptane derivatives in high stereoselectivity when the furan was alkyl substituted. On the other hand, the aryl-substituted furan cyclized via a completely different pathway to give spirocyclic and tricyclic products. (C) 2009 Elsevier Ltd All rights reserved. - ASYMMETRIC HYDROGENATION OF AROMATIC HETEROCYCLIC KETONES CATALYZED BY THE MsDPEN-Cp*Ir(III) COMPLEXNoriyuki Utsumi, Kunihiko Tsutsumi, Masahiko Watanabe, Kunihiko Murata, Noriyoshi Arai, Nobuhito Kurono, Takeshi OhkumeHETEROCYCLES 80 1 141 - 147 2010年01月 [査読有り][通常論文]
Asymmetric hydrogenation of aromatic heterocyclic ketones catalyzed by Cp*Ir(OTf)(Msdpen) (MsDPEN = N-(methanesulfonyl)-1,2-diphenylethylenediamine) affords the heterocyclic alcohols in 93% to >99% ee. The reaction is conducted in a methanolic solution with a substrate-to-catalyst molar ratio of 200-5000 under 15 atm of H-2. The heterocyclic rings of substrates are left intact. - Junichi Hori, Kunihiko Murata, Toshiki Sugai, Hisanori Shinohara, Ryoji Noyori, Noriyoshi Arai, Nobuhito Kurono, Takeshi OhkumaADVANCED SYNTHESIS & CATALYSIS 351 18 3143 - 3149 2009年12月 [査読有り][通常論文]
Palladium nanoparticles are prepared from palladium(II) acetate and 2 equivalents of potassium tert-butoxide in the presence of 4-octyne. The palladium nanoparticles-tetrabutylammonium borohydride system shows excellent catalytic activity and selectivity in the semihydrogenation of alkynes to the [(Z)-]alkenes. The hydrogenation of 4-octyne is conducted with the catalyst system at a substrate-to-palladium molar ratio of 10,000-200,000 under 8 atm of hydrogen to give (Z)-4-octene in > 99% yield. Isomerization and over-reduction of the Z-alkene are very slow even after consumption of the alkyne. - Kunihiko Tsutsumi, Takeaki Katayama, Noriyuki Utsumi, Kunihiko Murata, Noriyoshi Arai, Nobuhito Kurono, Takeshi OhkumaORGANIC PROCESS RESEARCH & DEVELOPMENT 13 3 625 - 628 2009年05月 [査読有り][通常論文]
Asymmetric hydrogenation of 3-quinuclidinone with RuBr(2)[(S,S)-xylskewphos](pica) in a base containing ethanol affords (R)-3-quinuclidinol in 88-90% ee (XylSkewphos = 2,4-bis(di-3,5-xylylphosphino)pentane, PICA = alpha-picolylamine). The optical purity of the product is readily increased to >99% by recrystallization. The hydrogenation of a 4.3-kg scale with a substrate-to-catalyst molar ratio of 100 000 under 15 atm of H(2) at 30-45 degrees C completes in 4 h. Use of methanol or 2-propanol as a solvent decreases the catalyst efficiency. RuCl(2)(skewphos)(pica), and RuCl(2)(tolbinap)(pica) which have similar structures, are less effective for this reaction. - Hirohito Ooka, Noriyoshi Arai, Keita Azuma, Nobuhito Kurono, Takeshi OhkumaJOURNAL OF ORGANIC CHEMISTRY 73 22 9084 - 9093 2008年11月 [査読有り][通常論文]
Asymmetric hydrogenation of acetophenone in the presence of Ru(II) catalysts coordinated by TolBINAP and a series of chiral 1,2-diamines was studied. The sense and degree of enantioselectivity were highly dependent on the N-substituents of the diamine ligands. The N-substituent effect was discussed in detail. Among these catalysts, the (S)-TolBINAP/(R)DMAPEN-Ru(II) complex showed the highest enantioselectivity. The mode of enantioface selection was interpreted by using transition state models based on the X-ray structure of the catalyst precursor. The chiral catalyst effected the hydrogenation of alkyl aryl ketones and arylglyoxal dialkyl acetals to afford the chiral alcohol in >99% ee in the best cases. Hydrogenation of racemic benzoin methyl ether with the chiral catalyst through dynamic kinetic resolution gave the anti-alcohol (syn:anti = 3:97) in 98% ee, while the reaction of alpha-amidopropiophenones resulted in the syn-alcohols (syn:anti = 96:4 to >99:1) in >98% ee. - Noriyoshi Arai, Takeshi OhkumaModern Reduction Methods 159 - 181 2008年04月04日 [査読有り][通常論文]
- Noriyoshi Arai, Keita Azuma, Noriyuki Nii, Takeshi OhkumaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 47 39 7457 - 7460 2008年 [査読有り][通常論文]
- Noriyoshi Arai, Ken Suzuki, Satoshi Sugizaki, Hiroko Sorimachi, Takeshi OhkumaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 47 9 1770 - 1773 2008年 [査読有り][通常論文]
- Takeshi Ohkuma, Noriyuki Utsumi, Masahito Watanabe, Kunihiko Tsutsumi, Noriyoshi Arai, Kunihiko MurataORGANIC LETTERS 9 13 2565 - 2567 2007年06月 [査読有り][通常論文]
Asymmetric hydrogenation of a series of alpha-hydroxy aromatic ketones in methanol catalyzed by Cp*Ir(OTf)(MsDPEN) (MsDPEN = N-(methanesulfonyl)-1,2-diphenylethylenediamine) affords the 1-aryl-1,2-ethanediols in up to 99% ee. The reaction can be conducted with a substrate-to-catalyst molar ratio as high as 6000 under 10 atm of H-2. 1-Hydroxy-2-propanone is also hydrogenated with high enantioselectivity. - Noriyoshi Arai, Hirohito Ooka, Keita Azuma, Toshio Yabuuchi, Nobuhito Kurono, Tsutomu Inoue, Takeshi OhkumaORGANIC LETTERS 9 5 939 - 941 2007年03月 [査読有り][通常論文]
A catalyst system consisting of RuCl2[(S)-tolbinap][(R)-dmapen] and t-C4H9OK in 2-propanol effects asymmetric hydrogenation of arylglyoxal dialkylacetals to give the alpha-hydroxy acetals in up to 98% ee. Hydrogenation of racemic alpha-amidopropiophenones under dynamic kinetic resolution predominantly gives the syn alcohols in up to 99% ee and > 98% de, while the reaction of racemic bezoin methyl ether gives the anti alcohols in excellent stereoselectivity. - Takeshi Ohkuma, Kunihiko Tsutsumi, Noriyuki Utsumi, Noriyoshi Arai, Ryoji Noyori, Kunihiko MurataORGANIC LETTERS 9 2 255 - 257 2007年01月 [査読有り][通常論文]
Asymmetric hydrogenation of various alpha-chloro aromatic ketones with Ru(OTf)(TsDPEN)(eta(6)-arene) (TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) produces the chiral chlorohydrins in up to 98% ee. This reaction can be conducted even on a 206-g scale. The hydrogenation of an alpha-chloro ketone with a phenol moiety has been utilized for the synthesis of (R)-norphenylephrine without protection-deprotection operations. - N Arai, M Iwakoshi, K Tanabe, K NarasakaBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 72 10 2277 - 2285 1999年10月 [査読有り][通常論文]
Aromatic and aliphatic nitrile oxides are generated by the oxidation of alpha-hydroxyimino carboxylic acid with ammonium hexanitratocerate(IV). They react with olefinic and acetylenic dipolarophiles to give the corresponding cycloaddition products in good yield. The oxidation of alpha-oxo aldoximes also affords alpha-oxo carbonitrile oxides. - M Miura, N Arai, K NarasakaBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 71 6 1437 - 1441 1998年06月 [査読無し][通常論文]
Oxidation of cyclohexane-l,2-dione with ammonium hexanitratocerate(Iv) (CAN) generates 2,3-dioxocyclohexyl radical, which reacts with electron-rich olefins to afford the corresponding addition products. The adducts thus generated are converted to 4,5-dihydro-7(6H)-benzofuranone by acid treatment. In addition to cydohexane-1,2-dione, radical species are also generated from cyclopentane-l,2-dione acid cycloheptane-1,2-dione. - N Arai, K NarasakaBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 70 10 2525 - 2534 1997年10月 [査読無し][通常論文]
1-Nitroalkyl radicals are generated by oxidation of potassium salt of 1-aci-nitroalkanes with ammonium hexanitratocerate(IV). When the oxidation is carried out in the presence of electron-rich olefins, such as silyl enol ethers, intermolecular addition of the radicals onto the olefins proceeds to afford beta-nitro ketones, which are further converted to alpha,beta-unsaturated ketones in high yield. Stereoselective construction of fused ring systems is achieved by intramolecular addition of 1-nitroalkyl radicals. - IKENO Taketo, HARADA Manabu, ARAI Noriyoshi, NARASAKA KoichiChemistry letters 2 169 - 170 1997年 [査読無し][通常論文]
Cation radicals, generated from alpha-stannyl sulfides by the photoinduced single electron transfer, cleave into alpha-alkylthio radical intermediates with the elimination of the stannyl group. The alpha-alkylthio radicals thus formed are utilized for carbon-carbon bond forming reactions. - N Arai, K NarasakaJOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN 54 11 964 - 975 1996年11月 [査読有り][通常論文]
By oxidation of beta-keto acids, cyclopropanols, and acyl chromate complexes with tris(2-pyridinecarboxylato)manganese(III) (Mn(pic)(3)), alpha-keto, beta-keto, and alkyl radicals are generated respectively, which react with olefinic compounds to afford intermolecular addition products in good yield. On the other hand, the cation radicals can be generated from alpha-stannylalkyl sulfides, alpha-stannylalkyl amine derivatives, and alpha-stannyl carboxylic eaters by oxidation with ammonium hexanitratocerate(IV) (CAN). These cation radicals of stannyl compounds readily cleave into carbocation or radical species, which are utilized as reactive intermediates for carbon-carbon bond formation. - ARAI Noriyoshi, NARASAKA KoichiChemistry letters 11 987 - 988 1995年11月 [査読無し][通常論文]
alpha-Nitroalkyl radicals are generated by oxidation of nitronate anions with cerium(IV) ammonium nitrate. When the reactions are carried out in the presence of electron-rich olefins, such as silyl enol ethers, intermolecular addition of the radicals proceeds to afford beta-nitroketones, which are further converted to alpha,beta-unsaturated ketones in good yield. - N ARAI, K NARASAKABULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 68 6 1707 - 1714 1995年 [査読有り][通常論文]
The one-electron oxidation of alpha-(arylazo)triphenylmethanes by cerium(IV) ammonium nitrate (CAN) generated aryl radicals along with the triphenylmethyl cation. When the reaction was carried out in the presence of appropriate radical-trapping agents, such as arenes and olefins, the corresponding addition products were obtained in moderate yield. The oxidation of the arylazo compounds with CAN was accelerated by the addition of acids. - K NARASAKA, N ARAI, T OKAUCHIBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 66 10 2995 - 3003 1993年10月 [査読有り][通常論文]
2-'Tributylstannyl-1,3-dithianes and 1- (tributylstannyl)alkyl sulfides are oxidized with ammonium hexanitratocerate(IV) or ferrocenium hexafluorophosphate to generate their cation radicals, which dissociate into the carbocations and tributylstannyl radical. The carbocations thus generated react with olefinic nucleophiles to afford the corresponding addition products in good yield. - K NARASAKA, T OKAUCHI, N ARAICHEMISTRY LETTERS 7 1229 - 1232 1992年07月 [査読無し][通常論文]
Oxidation of 2-tributylstannyl-1,3-dithianes with metallic oxidants generates reactive species such as 1,3-dithian-2-yl radical and/or cation by eliminating the stannyl group. Those intermediates react with olefins to give the intermolecular addition products.
書籍
- 有機合成実験法ハンドブック大熊毅, 新井則義 (担当:共著範囲:25.1.4 還元法―水素ガスを用いる―触媒の調製と反応例)
丸善 2015年 - e-EROS Encyclopedia of Reagents for Organic SynthesisOhkuma, Takeshi, Arai, Noriyoshi (担当:共著範囲:Phosphine, 1,1'-(1R)-[1,1'-binaphtharene]-2,2'-diylbis[bis(4-methylphenyl)-; Phosphine, 1,1'-(1S)-[1,1'-binaphtharene]-2,2'-diylbis[bis(4-methylphenyl)-)
Wiley Online Library 2014年 - Comprehensive ChiralityOhkuma, Takeshi, Arai, Noriyoshi (担当:共著範囲:Reduction–Hydrogenation: C=O; Chemoselective)
Elsevier 2012年 - Science of Synthesis, Stereoselective Synthesis 2Arai, Noriyoshi, Ohkuma, Takeshi (担当:共著範囲:Reduction of Carbonyl Groups: Hydrogenation)
Thieme 2010年 - 触媒便覧大熊毅, 新井則義 (担当:共著範囲:17.6.2不斉水素化反応)
講談社サイエンティフィク 2008年 - Modern Reduction MethodsArai, Noriyoshi, Ohkuma, Takeshi (担当:共著範囲:Carbonyl Hydroboration)
Wiley-VCH 2008年
講演・口頭発表等
- Generation of Molecular Complexity by Photochemical Activation of 5-Membered Heteroaromatics [招待講演]Noriyoshi Arai18th Malaysian International Chemical Congress 2014年11月 口頭発表（招待・特別）
- Enantioselective 1,3-Hydrogen Migration of Primary Allylic Alcohols Catalyzed by Diphosphine–Ru(II) Complexes [通常講演]Arai, Noriyoshi, Sato, Keisuke, Ohkuma, Takeshi26th International Conference on Organometallic Chemistry 2014年07月 口頭発表（一般）
その他活動・業績
- 大熊毅,新井則義 Bulletin of the Chemical Society of Japan 92 (3) 475 -504 2019年 [査読有り][通常論文]
Two types of chiral Ru(II) complexes, each with two kinds of ligands, have been designed and utilized as catalysts for several asymmetric reactions under appropriate conditions. The first type, the diphosphine/diamine-Ru(II)-type complexes, were found to catalyze the hydrogenation of a variety of simple and functionalized ketones as well as imino compounds with high activity and enantioselectivity. The double asymmetric hydrogenation of alpha,beta-unsaturated ketones into the chiral saturated alcohols was achieved by using the dual catalyst system, which reversibly forms two catalytic species. The asymmetric isomerization of primary allylic alcohols into the optically active aldehydes with almost perfect enantioselectivity was realized with this type of catalyst. The second type, the amino acid/diphosphine-Ru(II)-type complexes combined with Li compounds, exhibited excellent catalyst performance in the asymmetric cyanosilylation of aldehydes as well as simple and functionalized ketones. The isolated Ru.Li bimetallic complexes were suitable for the asymmetric hydrocyanation of aldehydes. This combined system was applicable to the asymmetric conjugate hydrocyanation of alpha,beta-unsaturated ketones and carboxylic acid derivatives, and the Strecker-type reaction of the pi-isoelectronic N-alkoxycarbonyl aldimines. This account describes the concept underlying the design of these catalysts, and the catalyst performance in the asymmetric reactions. - 基礎講座：有機合成化学(1) 有機化合物の作り方事始め新井則義, 大熊毅 現代化学 (560) 17 -21 2017年11月 [査読無し][招待有り]
- Noriyoshi Arai, Takeshi Ohkuma CHEMICAL RECORD 12 (2) 284 -289 2012年04月 [査読有り][通常論文]
Development of highly active catalysts has been an important research area in synthetic chemistry, especially from a practical point of view. Herein, we focus on the homogeneous catalytic hydrogenation using well-defined molecular catalysts and discuss recent advances in the field with regard to the turnover number for these catalysts. DOI 10.1002/tcr.201100019 - 新井 則義, 力石 典子, 大村 智, 桑嶋 功 天然有機化合物討論会講演要旨集 0 (44) 19 -24 2002年09月01日 [査読無し][通常論文]
Kazusamycin, which was isolated as a metabolite of actinomycete strain 81-484, attracts much attention due to its potent antitumor activity on P388 leukemia and sarcoma 180. It was also effective in completely preventing growth of HeLa cells at a concentration of 3.3ng/ml. On the other hand, from the structural point of view, only its planar structure was elucidated, and both its absolute configuration and complete relative configuration remain unknown. We are making an effort on the total synthesis of Kazusamycin in order to determine its absolute configuration and to establish a practical... - 新井 則義 化学と工業 = Chemistry and chemical industry 54 (4) 492 -492 2001年04月01日 [査読無し][通常論文]
共同研究・競争的資金等の研究課題
- 光による分子活性化を活用した高立体選択的有機分子構築手法の開発日本学術振興会：科学研究費助成事業，基盤研究C研究期間 : 2013年04月 -2015年03月代表者 : 新井則義
- 日本学術振興会：科学研究費助成事業研究期間 : 1997年 -1998年代表者 : 新井 則義筆者は,α-ヒドロキシイミノカルボン酸に対し,アルケン,またはアルキン類の存在下,硝酸アンモニウムセリウム(IV)(CAN)を作用させることによりニトリルオキシドを生成し,対応する付加生成物として4,5-ジヒドロイソオキサゾール,あるいはイソオキサゾール誘導体がそれぞれ得られることをすでに見出している。今年度の検討において,ニトリルオキシドの前駆体としてα-ヒドロキシイミノカルボン酸のみならず2-オキソアルドキシムも有効に活用でき,アシル(アロイル)ニトリルオキシドの発生に利用できることを見出した。たとえば,フェニルグリオキサール-1-オキシムに対しアクリル酸エチルの存在下CANを作用させると,生じたベンゾイルニトリルオキシドとアクリル酸エチルとの環状付加反応が進行し,3-ベンゾイル-4,5-ジヒドロイソオキサゾール-5-カルボン酸エチルが85%の収率で得られる。アシル(アロイル)ニトリルオキシドの効率の良い発生手法についてはわずかしか報告例がないが,本手法を用いることにより3-アシルイソオキサゾール誘導体を収率良く合成することができる。さらに,2-オキソアルドキシムに代え2-オキソアルデヒド-1-ヒドラゾンを用いれば,ニトリルオキシドと同様1,3-双極子の一種であるニトリルイミンを発生させることも可能なのではないかと考え,フェニルグリオキサール-1-アセチルヒドラゾンに対し,CANを作用させ反応を試みた。その結果,オレフィンとの付加生成物は得られなかったものの,自己環化生成物である1,3,4-オキサジアゾール誘導体が得られた。この化合物はニトリルイミンの発生を示唆するものと考えられる。
教育活動情報
主要な担当授業
- 有機反応・構造論開講年度 : 2021年課程区分 : 修士課程開講学部 : 総合化学院キーワード : 分子軌道，化学結合，反応中間体，立体化学，分子認識，分子集合体，ペリ環状反応，Woodward-Hoffmann則，環化付加反応，電子環状反応，シグマトロピー転位，グループ移動反応
- 英語演習開講年度 : 2021年課程区分 : 学士課程開講学部 : 全学教育キーワード : 英語，化学，工学
- 有機化学Ⅱ開講年度 : 2021年課程区分 : 学士課程開講学部 : 工学部キーワード : ハロゲン化アルキル、共役ジエン、芳香族化合物、アルコール、エーテル
- 応用化学学生実験Ⅴ開講年度 : 2021年課程区分 : 学士課程開講学部 : 工学部キーワード : 有機化学、高分子化学、安全教育、基礎実験、合成実験
- 物質変換工学開講年度 : 2021年課程区分 : 学士課程開講学部 : 工学部キーワード : 有機合成，有機材料，化学プロセス，反応器設計，生体材料，高分子材料，分子機能，無機材料，複合材料，電子材料，光機能材料