研究者データベース

大西 英博(オオニシ ヨシヒロ)
薬学研究院 創薬科学部門 創薬化学分野
准教授

基本情報

所属

  • 薬学研究院 創薬科学部門 創薬化学分野

職名

  • 准教授

学位

  • 博士(薬学)(北海道大学)

ホームページURL

J-Global ID

研究キーワード

  • 有機合成化学   有機金属化学   

研究分野

  • ライフサイエンス / 薬系化学、創薬科学

職歴

  • 2016年 - 現在 北海道大学 大学院薬学研究院 准教授
  • 2015年 - 2016年 北海道大学 大学院薬学研究院 講師
  • 2007年 - 2015年 北海道大学 大学院薬学研究院 助教
  • 2006年 - 2007年 北海道大学 大学院薬学研究院 助手
  • 2005年 - 2006年 北海道大学 大学院薬学研究科 助手

所属学協会

  • 近畿化学協会   有機合成化学協会   日本化学会   日本薬学会   

研究活動情報

論文

  • Yoshihiro Oonishi, Yoshihiro Sato, Shunki Sakamoto, Shuya Agata
    Synthesis 53 17 2976 - 2983 2021年09月 [査読有り][招待有り]
     
    AbstractRhodium(I)-catalyzed enantioselective cyclization of enynes through C(sp3)–H bond activation was investigated. It was found that the cyclization of enynes having a tert-butyl moiety on the alkene afforded a spirocyclic compound (up to 92% ee), while the cyclization of enynes having an isopropyl or an ethyl group on the alkene gave a cyclic diene (up to 98% ee). Furthermore, an intermolecular competition reaction using a deuterium-labeled substrate revealed that C(sp3)–H bond activation was one of the key steps, having a high energy barrier, in this cyclization.
  • Souta Misawa, Asaki Miyairi, Yoshihiro Oonishi, Yoshihiro Sato, Steven P. Nolan
    Synthesis 53 24 4644 - 4653 2021年07月27日 [査読有り][通常論文]
     
    AbstractPolarized alkynes such as ynol ethers and ynamides have attracted much attention due to their inherent unique reactivity. Herein, we report Au(I)-catalyzed hydroalkoxylation/Claisen rearrangement cascade reactions of aryl ynol ethers and ynamides with allylic alcohols. At the first stage (hydroalkoxylation) of this cascade reaction, attack of allylic alcohols to aryl ynol ethers or ynamides occurs at the α-position of the polarized alkynes in a completely regioselective manner. Claisen rearrangement of the resulting adducts subsequently takes place to give γ,δ-unsaturated esters or amides, respectively. The [Au(IPr)NTf2] catalyst is most effective for this reaction, and the reaction proceeds under mild conditions (in the case of aryl ynol ether: in THF, 60 °C; in the case of ynamides: in toluene, 80 °C) in an atom-economical way.
  • Asaki Miyairi, Yoshihiro Oonishi, Yoshihiro Sato
    Organic & Biomolecular Chemistry 19 43 9396 - 9400 2021年 [査読有り][通常論文]
     
    One-pot synthesis of fully substituted 2-aminofurans via a Au(I)-catalyzed cascade reaction of ynamides and propargylic alcohol was realized. Hydroalkoxylation of ynamide with propargylic alcohol, Saucy-Marbet rearrangement, and cyclization of the...
  • Yoshihiro Oonishi, Akihito Hosotani, Takayuki Yokoe, Yoshihiro Sato
    ORGANIC LETTERS 21 11 4120 - 4123 2019年06月 [査読有り][通常論文]
     
    Rhodium(I)-catalyzed enantioselective hydro-acylation of 4-allenals was found to proceed smoothly, giving six-membered ketones in good yields (up to 84% yield) with high enantiomeric excess (up to 96% ee) even from racemic allenes as substrates. Mechanistic studies revealed that racemization of the allene moiety in the substrate would occur via a dynamic kinetic resolution (DKR) process during the hydroacylation.
  • Yoshihiro Oonishi, Shuichi Masusaki, Shunki Sakamoto, Yoshihiro Sato
    Angewandte Chemie International Edition 58 26 8736 - 8739 Wiley 2019年05月 [査読有り][通常論文]
  • Yoshio Hato, Yoshihiro Oonishi, Yasunori Yamamoto, Kiyohiko Nakajima, Yoshihiro Sato
    JOURNAL OF ORGANIC CHEMISTRY 81 17 7847 - 7854 2016年09月 [査読有り][通常論文]
     
    Stereoselective construction of spiro-fused tricyclic compounds from enynes having a tethered imine with diazoalkenes was achieved by Rh(I)- and Rh(II)-catalyzed sequential reactions. This method consists of three reactions, Rh(I)-catalyzed cyclization of enynes with a tethered imine, Rh(II)-catalyzed cyclopropanation with diazoalkenes, and Cope rearrangement. Notably, the sequential reactions can be operated in one pot, in which Rh(I) and Rh(II) catalysts work in relay without any serious catalyst deactivation to afford the spirocycles in a stereoselective manner.
  • Yoshihiro Oonishi, Yoshio Hato, Yoshihiro Sato
    ADVANCED SYNTHESIS & CATALYSIS 358 14 2273 - 2279 2016年07月 [査読有り][通常論文]
     
    The rhodium(I)-catalyzed cycloisomerization of enynes with tethered (S)-2-methyl-2-propanesulfinyl imine affords 5- or 6-membered cyclic compounds containing exocyclic 1,3-diene moieties in a stereoselective manner. The reaction proceeds through beta-hydride elimination of a 7-membered azarhodacycle intermediate, which is generated from three unsaturated bonds (i.e., alkene, alkyne, and C=N bonds) and an Rh(I) complex. The resultant cyclic compounds could be reacted with various dienophiles to afford spiroamides as single isomers through the Diels-Alder reaction.
  • Adrian Gomez-Suarez, Yoshihiro Oonishi, Anthony R. Martin, Steven P. Nolan
    BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY 12 172 - 178 2016年02月 [査読有り][通常論文]
     
    Due to the synthetic advantages presented by the dual-gold-catalysed hydrophenoxylation of alkynes, a thorough study of this reaction was carried out in order to fully define the scope and limitations of the methodology. The protocol tolerates a wide range of functional groups, such as nitriles, ketones, esters, aldehydes, ketals, naphthyls, allyls or polyphenols, in a milder and more efficient manner than the previously reported methodologies. We have also identified that while we are able to use highly steric hindered phenols, small changes on the steric bulk of the alkynes have a dramatic effect on the reactivity. More importantly, we have observed that the use of substrates that facilitate the formation of diaurated species such as gem-diaurated or sigma,pi-digold-acetylide species, hinder the catalytic activity. Moreover, we have identified that the use of directing groups in unsymmetrical alkynes can help to achieve high regioselectivity in the hydrophenoxylation.
  • Adrian Gomez-Suarez, Yoshihiro Oonishi, Anthony R. Martin, Sai V. C. Vummaleti, David J. Nelson, David B. Cordes, Alexandra M. Z. Slawin, Luigi Cavallo, Steven P. Nolan, Albert Poater
    CHEMISTRY-A EUROPEAN JOURNAL 22 3 1125 - 1132 2016年01月 [査読有り][通常論文]
     
    Herein, we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)}(2)(mu-OH)][BF4] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non-coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co-catalyst, lowering the energy barriers of several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an "off-cycle" rather than an "in-cycle" intermediate.
  • Yoshihiro Oonishi, Yoshio Hato, Yoshihiro Sato
    ADVANCED SYNTHESIS & CATALYSIS 357 14-15 3033 - 3039 2015年10月 [査読有り][通常論文]
     
    The rhodium(I)-catalyzed intramolecular [2+2+2] cycloaddition between allenes, alkynes, and imines has been developed. This cyclization proceeds via a strained azarhodacycle, giving a 5,7-fused cyclic amide or a tricyclic product containing an 8-azabicyclo[3.2.1] octane skeleton in high yield.
  • Yoshihiro Oonishi
    CHEMICAL & PHARMACEUTICAL BULLETIN 63 6 397 - 407 2015年06月 [査読有り][通常論文]
     
    Novel Rh(I)-catalyzed cyclizations through a different type of rhodacycle intermediate which is formed by hydroacylation of 4,6-dienal or oxidative addition of diene and alkene are described. Hydroacylation of 4,6-dienal afforded various 7-membered rings in good to high yields, while cycloisomerization of diene and alkene provided 5- or 6-membered rings in good yields. On the basis of these studies, we have also succeeded in developing the sequential reaction of hydroacylation followed by cycloisomerization to produce bicyclic compounds in a stereoselective manner and thus this reaction was expanded to the synthesis of epiglobulol. Furthermore, both Rh(I)-catalyzed hydroacylation and cycloisomerization using ionic liquid (IL) as a solvent were investigated and it was found that the IL recovered after the reaction, which contains the Rh(I) catalyst, could be recycled several times without loss of catalytic activity.
  • Yoshihiro Oonishi, Akira Saito, Yoshihiro Sato
    ASIAN JOURNAL OF ORGANIC CHEMISTRY 4 1 81 - 86 2015年01月 [査読有り][通常論文]
     
    Rhodium(I)-catalyzed cyclization of allenyl aldehydes with various alkynes was investigated. The cyclizations of internal alkynes that have both an electron-rich aromatic ring and an electron-withdrawing group at the terminus afforded [2+2+2] cycloaddition products in good yields with good to high regio- and enantioselectivity, while the reactions of terminal alkynes gave dienyl ketones instead of [2+2+2] cycloaddition products in good yields. These results indicate that the nature of the alkynes greatly influences the reaction course.
  • Yoshihiro Oonishi, Adrian Gomez-Suarez, Anthony R. Martin, Yusuke Makida, Alexandra M. Z. Slawin, Steven P. Nolan
    CHEMISTRY-A EUROPEAN JOURNAL 20 42 13507 - 13510 2014年10月 [査読無し][招待有り]
     
    A new synthetic protocol that combines the advantages offered by eco-friendly solvent-free reactions and sequential transformations is reported. This strategy offers straightforward access to benzo[c]chromenes and benzo[b]furans from commercially available starting materials. This two-step, one-pot strategy consists of an Au-catalyzed hydrophenoxylation process followed by Pd-catalyzed CH activation or Mizoroki-Heck reactions. The selectivity of the process towards CH activation or Mizoroki-Heck reaction can be easily tuned.
  • Yoshihiro Oonishi, Takayuki Yokoe, Akihito Hosotani, Yoshihiro Sato
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 53 4 1135 - 1139 2014年01月 [査読無し][招待有り]
     
    Rhodium(I)-catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp(2))-rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8-oxabicyclo[3.2.1]octane skeleton, while -hydride elimination from the same intermediate gives products that contain fused five- and seven-membered rings in high yields.
  • Yoshihiro Oonishi, Yoshitaka Kitano, Yoshihiro Sato
    TETRAHEDRON 69 36 7713 - 7718 2013年09月 [査読無し][通常論文]
     
    Rh(I)-catalyzed intramolecular [2+2+2] cycloaddition of allenynes with tethered aldehydes was investigated. The cyclizations proceeded smoothly under mild conditions to give various tricyclic compounds containing a pyran ring in good to high yields in a stereoselective manner. (C) 2013 Elsevier Ltd. All rights reserved.
  • Yoshihiro Oonishi, Adrian Gomez-Suarez, Anthony R. Martin, Steven P. Nolan
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 52 37 9767 - 9771 2013年09月 [査読無し][通常論文]
  • Adrian Gomez-Suarez, Yoshihiro Oonishi, Sebastien Meiries, Steven P. Nolan
    ORGANOMETALLICS 32 4 1106 - 1111 2013年02月 [査読無し][通常論文]
     
    The synthesis of a series of digold hydroxide complexes is reported. These diaurated species, of the formula [{Au(NHC)}(2)(mu-O)][BF4] (where NHC = IPrCl, IPr*, IPent), were easily prepared via the cationic species [Au(NHC)-(NCCH3)][BF4] in aqueous media. The catalytic activity of these novel complexes was tested and compared to that of the previously reported IPr and SIPr derivatives. These digold hydroxide species are highly active in water-inclusive organic transformations, such as the alkyne and nitrile hydration reactions, and the Meyer-Schuster rearrangement. One salient feature of these systems is the lack of any additive to induce catalytic activity.
  • Alba Collado, Adrian Gomez-Suarez, Yoshihiro Oonishi, Alexandra M. Z. Slawin, Steven P. Nolan
    CHEMICAL COMMUNICATIONS 49 91 10745 - 10747 2013年 [査読有り][通常論文]
     
    The synthesis of a new class of organogold species containing a peroxo moiety is reported. Complexes [Au(IPr)((OOBu)-Bu-t)] and [Au(SIPr)((OOBu)-Bu-t)] have been synthesised via a straightforward methodology using the parent gold(I) hydroxide complexes as synthons. These complexes have been successfully used in oxygen-transfer reactions to triphenylphosphine.
  • Oonishi Y, Kitano Y, Sato Y
    Angewandte Chemie (International ed. in English) 51 29 7305 - 7308 29 2012年 [査読有り][通常論文]
  • Yoshihiro Oonishi, Akihito Hosotani, Yoshihiro Sato
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 51 46 11548 - 11551 2012年 [査読有り][通常論文]
  • Yoshihiro Oonishi, Akihito Hosotani, Yoshihiro Sato
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 133 27 10386 - 10389 2011年07月 [査読有り][通常論文]
     
    Rh(I)-catalyzed formal [6 + 2] cycloaddition of allenal 6 having an alkyne or alkene in a tether proceeded smoothly, giving 5-8- and 6-8-fused bicyclic ketone derivatives 7 in good to excellent yields. It was also found that cyclization of enantiomerically enriched (S)-6a (94% ee) gave cyclic ketone derivative (S)-7a in high yield with reasonable chirality transfer (86% ee). This result indicates that this cyclization proceeds through stereoselective formation of rhodacycle H' followed by insertion of a multiple bond.
  • Takashi Mizuno, Yoshihiro Oonishi, Masanori Takimoto, Yoshihiro Sato
    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY 2011 14 2606 - 2609 2011年05月 [査読無し][通常論文]
     
    The total synthesis of (-)-corynantheidine has been achieved through Ni(0)-mediated carboxylative cyclization as the key reaction step with incorporation of CO(2), and this cyclization was also successfully expanded to the catalytic reaction by using Et(2)Zn in the presence of an excess amount of DBU.
  • Yoshihiro Oonishi, Ai Taniuchi, Yoshihiro Sato
    SYNTHESIS-STUTTGART 17 2884 - 2892 2010年09月 [査読無し][通常論文]
     
    We previously developed a novel rhodium(I)-catalyzed cascade reaction involving the hydroacylation of a 4,6-dienal followed by cycloisomerization of the resulting 1,3-diene with an alkene, giving carbocycles containing a bicyclo[5.3.0]decenone skeleton in a stereoselective manner. Herein, we report the construction of the C(5), C(7), C(6)-tricyclic core of guanacastepenes using this cascade reaction.
  • Yoshihiro Oonishi, Akira Saito, Miwako Mori, Yoshihiro Sato
    SYNTHESIS-STUTTGART 6 969 - 979 2009年03月 [査読無し][通常論文]
     
    A rhodium(I)-catalyzed cycloisomerization of 1,3-dienes with alkenes in a tether proceeded smoothly, giving cyclopentene or cyclohexene derivatives in good yields. The existence of a hetero atom between the 1,3-diene moiety and the olefin in the tether affected the reaction Course. In the case of the substrate having no hetero atom between the 1,3-diene moiety and olefin in the tether, cycloisomerization reaction proceeded, giving the corresponding cyclic product. On the other hand, in the case of the substrate having a hetero atom between the 1,3-diene moiety and olefin in the tether, the reaction course was completely changed to give a [4+2] cycloaddition product.
  • Yoshihiro Oonishi, Akira Saito, Yoshihiro Sato
    GREEN CHEMISTRY 11 3 330 - 333 2009年 [査読無し][通常論文]
     
    A Rh(I)-catalyzed cycloisomerization of dienes with alkenes using ionic liquids (ILs) as reaction media was investigated. In contrast to the hydroacylation promoted by the same cationic Rh(I) catalyst, the structure of ILs strongly affected the recyclability of the catalyst in this cycloisomerization, and a [BDMI (1-butyl-2,3-dimethyl imidazolium)](+)-based IL was more effective than a [BMI (1-butyl-3-methyl imidazolium)](+)-based one. It has also been proven that the addition of 2,2,2-trifluoroethanol (TFE) to the reaction mixture prevented the loss of reactivity of the catalyst, and the IL recovered after the reaction under the present conditions could be used repeatedly.
  • Hiroki Yamamoto, Yoshihiro Oonishi, Yoshibiro Sato
    HETEROCYCLES 76 2 1485 - 1495 2008年11月 [査読無し][通常論文]
     
    A Pd(0)-catalyzed asymmetric deconjugative allylation of various Knoevenagel products and allylic compounds was investigated. It was found that various compounds, having a quaternary carbon center directly attached to sp(2)-carbon centers including a 1,3-diene moiety, could be synthesized through this methodology, although the yield and enantiomeric excess varied from low to modest depending on the structure of substrates and the reaction conditions.
  • Yoshihiro Sato, Yu Hinata, Reiko Seki, Yoshihiro Oonishi, Nozomi Saito
    ORGANIC LETTERS 9 26 5597 - 5599 2007年12月 [査読有り][通常論文]
     
    Nickel(0)-catalyzed asymmetric three-component coupling of 1,3-dienes, aldehydes, and silanes has been realized utilizing a chiral N-heterocyclic. carbene as a ligand. On the basis of the screening of various NHC precursors, an imidazolium salt having 1-(2,4,6-trimethylphenyl)propyl groups on the nitrogen was designed and synthesized. In this reaction, various coupling products were produced in good yields with high regio-, diastereo- (anti selective in the case of the internal 1,3-diene), and enantioselectivities (up to 97% ee).
  • Yoshihiro Oonishi, Jiro Ogura, Yoshihiro Sato
    TETRAHEDRON LETTERS 48 42 7505 - 7507 2007年10月 [査読無し][通常論文]
     
    Rh(I)-catalyzed hydroacylation of 4-alkenal or 4,6-dienal using ionic liquids (ILs) as reaction media proceeded smoothly, giving cyclopentanone or cycloheptenone derivatives in good yields. It was found that the IL recovered after the reaction, which should contain the Rh(I) catalyst, could be recycled 5-10 times without the loss of catalytic activity and enantioselectivity (in the case of asymmetric hydroacylation). (C) 2007 Elsevier Ltd. All rights reserved.
  • 大西 英博, 谷内 亜衣, 佐藤 美洋
    天然有機化合物討論会講演要旨集 49 503 - 508 天然有機化合物討論会 2007年08月24日 
    We have recently reported a novel Rh(I)-catalyzed cascade reaction by combination of a hydroacylation of 4,6-dienal and a cycloisomerization of the resultant triene, giving a bicyclo[5.3.0]decenone derivative (Scheme 1). By the use of the cascade reaction, the synthesis of (±)-epiglobulol has been also accomplished. Herein, we report the construction of polycyclic compounds using the Rh(I)-catalyzed cascade reaction with the aim of the synthesis of Guanacastepenes (Scheme 2). Treatment of syn-3 with 10 mol% of [Rh(dppe)]ClO4 in dichloroethane at 65 ℃ for 6 h gave the desired tricyclic compound syn-4 in 34% yield along with syn-S, anti-4, and anti-5 in 8%, 7%, and 23% yields, respectively (Scheme 3). It was thought that bicyclic compound syn-5 was formed through reductive elimination from 6 (Scheme 4). On the other hand, anti-4, and anti-5 should be produced from anti-3, which would be formed from syn-3 via epimerization of a-proton of the aldehyde moiety syn-3. In the cyclization of anti-3 under the same conditions, bicyclic compound anti-5 was produced as the major product in 32% yield and the desired tricyclic compound anti-4 was produced in only 9% yield. These results indicate that the stereochemistry of cyclohexane ring in 3 affects on the reaction course. In order to prevent the isomerization of syn-3 to anti-3, the reactions of syn-3 were examined under the various conditions (Table 1). It was found that the cyclization of syn-3 in the presence of MS 4A gave the cyclized product syn-4 in 61% yield as the major product, while anti-4 and anti-5 derived from anti-3 were not obtained.
  • Yoshihiro Oonishi, Miwako Mori, Yoshihiro Sato
    SYNTHESIS-STUTTGART 15 2323 - 2336 2007年08月 [査読無し][通常論文]
     
    Rhodium(I)-catalyzed hydroacylation of 4,6-dienals was investigated. Hydroacylation of 4,6-dienals with a substituent at the C7 position produced cycloheptenone derivatives as the major products, while the cyclization of 4,6-dienals with no substituent at the terminus of the diene moiety preferentially gave cyclopentanone derivatives. The olefinic geometry of the diene moiety in 4,6-dienals also affected the reaction course, and the cyclization of substrates with an E-olefin at the C6 position produced cycloheptenone derivatives as the major products, while a cyclopentanone derivative was obtained from a substrate with a Z-olefin at the C6 position.
  • Yoshihiro Oonishi, Ai Taniuchi, Miwako Mori, Yoshihiro Sato
    TETRAHEDRON LETTERS 47 32 5617 - 5621 2006年08月 [査読無し][通常論文]
     
    A novel Rh(I)-catalyzed cascade reaction was developed by combination of a hydroacylation of 4,6-dienal and a cycloisomerization of the resultant triene, giving the bicyclo[5.3.0]decenone derivative 8b in a stereoselective manner. It was found that the Thorpe-Ingold effect played an important role in the second cycloisomerization step of this cascade cyclization. From the cascade cyclization product, (+/-)-epiglobulol could be synthesized. (c) 2006 Elsevier Ltd. All rights reserved.
  • O Navarro, N Marion, Y Oonishi, RA Kelly, SP Nolan
    JOURNAL OF ORGANIC CHEMISTRY 71 2 685 - 692 2006年01月 [査読無し][通常論文]
     
    [GRAPHICS] The activity of the complex (IPr)PdCl(eta(2)-N,C-C(12)H(7)NMe(2)), 1 [IPr = (N,N'-bis(2,6-diisopropylphenyl)-imidazol)-2-ylidene], in the Suzuki-Miyaura cross-coupling reaction involving unactivated aryl chlorides and triflates with arylboronic acids at room temperature in technical, grade 2-propanol is described. These conditions allow for the synthesis of di- and tri-ortho-substituted biaryls in very short reaction times. This complex also displays very high activity for (x-ketone arylation and dehalogenation reactions of activated and unactivated aryl chlorides.
  • O Navarro, Y Oonishi, RA Kelly, ED Stevens, O Briel, SP Nolan
    JOURNAL OF ORGANOMETALLIC CHEMISTRY 689 23 3722 - 3727 2004年11月 [査読有り][通常論文]
     
    The reaction. profile of a series of palladium-based catalysts was examined in the Suzuki-Miyaura reaction using technical grade 2-propanol as solvent and potassium t-butoxide as base. The results generally show high activity. The method allows for the coupling of electron-rich aryl chlorides with sterically hindered aryl boronic acids to produce tri-ortho-substituted biaryls in high yields using very mild conditions and short reaction times. (C) 2004 Elsevier B.V. All rights reserved.
  • Y Sato, Y Oonishi, M Mori
    JOURNAL OF ORGANIC CHEMISTRY 68 25 9858 - 9860 2003年12月 [査読有り][通常論文]
     
    Palladium(0)-catalyzed deconjugative allylation of alkenylidenemalonates and alkylidenemalonates was achieved for the first time. Reactions of dimethyl 2-((E)-but-2-enylidene)malonate with various allylic acetates using LHMDS as a base in DMF in the presence of Pd(2)dba(3) (2.5 mol %) and PPh3 (10 mol %) proceeded at room temperature to give the corresponding alpha-allylation products in good yields in a regio- and stereoselective manner. This reaction can also be used for allylation of dimethyl ethylidenemalonate or dimethyl 2-((E)-pent-2-enylidene)malonate and give the desired a-allylation products in good yields.
  • Y Sato, Y Oonishi, M Mori
    ORGANOMETALLICS 22 1 30 - 32 2003年01月 [査読有り][通常論文]
     
    Rh(I)-catalyzed cycloisomerization of 1,3-dienes with alkenes in a tether proceeded smoothly, giving cyclopentene derivatives in good yields. It was interesting that the existence of a heteroatorn between a 1,3-diene moiety and alkene in the tether affected the reaction course and that only a [4 + 2] cycloaddition product was produced.
  • Y Sato, Y Oonishi, M Mori
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 41 7 1218 - + 2002年 [査読有り][通常論文]

その他活動・業績

受賞

  • 2015年02月 有機合成化学協会 有機合成化学協会 旭化成ファーマ研究企画賞
     実用的なトリフルオロメチル化反応の確立を指向した新規銅触媒の創製 
    受賞者: 大西英博
  • 2014年03月 日本薬学会 日本薬学会奨励賞
     ローダサイクル中間体を経由する環化反応の開発と有機合成への応用 
    受賞者: 大西英博
  • 2010年02月 日本化学会 優秀講演賞(学術)
     ロジウム触媒によるアレン-インとアルデヒドの分子内環化反応を利用した二環式化合物の合成 
    受賞者: 大西英博

共同研究・競争的資金等の研究課題

  • ロジウム触媒による基質のラセミ化を利用した光学活性環状化合物の合成
    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 : 2020年04月 -2023年03月 
    代表者 : 大西 英博
  • 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 : 2017年04月 -2020年03月 
    代表者 : 大西 英博
     
    ロジウム触媒よるアリルアルコールの異性化反応はこれまで詳細に研究されてきた。今回、本研究代表者はこの反応の鍵中間体であるオキサパイアリル中間体を利用した新たな反応の開発を検討した。その結果、アリルアルコールを側鎖に持つエニンと光学活性なロジウム触媒を反応させると、四置換炭素を持つ5員環化合物が良好な収率および不斉収率で生成することを見出すとともに、本反応を分子間反応へと展開した。また、本反応を検討中に、ロジウム触媒によるアリルアルコールの異性化、続くヒドロアシル化反応により7員環化合物が生成する新たな反応も見出した。さらに、C-H結合活性化を伴う触媒的不斉環化反応の開発にも成功した。
  • 文部科学省:科学研究費補助金(基盤研究(C))
    研究期間 : 2014年 -2016年 
    代表者 : 大西 英博
  • 文部科学省:科学研究費補助金(基盤研究(C))
    研究期間 : 2012年 -2014年 
    代表者 : 大西 英博
  • 文部科学省:科学研究費補助金(若手研究(B))
    研究期間 : 2010年 -2011年 
    代表者 : 大西 英博
     
    本研究代表者は、含窒素ヘテロ環カルベン、いわゆるNHCを配位子に持つロジウム触媒とアレンインとアルデヒドとの環化反応を検討したところ、5員環と8員環もしくは6員環と8員環が縮環した二環式化合物が良好な収率で生成することを見いだし報告した。そこで、本年度は本反応を分子間反応へと展開すべく検討を行った。すなわち、ロジウム触媒存在下、4-アレナールとアルキンの反応を行なった。その結果、本反応は末端アルキンを用いると立体選択的に進行し、目的とする8員環化合物が良好な収率で生成することがわかった。また、様々な官能基を有するアルキンや4-アレナールが適用可能であることも明らかにした。さらに、アルキンとしてアセチレンの利用も検討した。この場合も、反応は速やかに進行し対応する8員環化合物が高い収率で生成することも見いだした。ところで、先の分子内反応を検討中に、配位子としてdppeを用いると6員環と7員環が縮環した二環式アルコールが選択的に生成することを明らかにしていた。そこで、この反応の収率の向上を目指し、検討したところ、アルキンとアレンを繋ぐ炭素鎖が2炭素である基質を用いて反応を行なうと、良好な収率で二環式アルコールが生成することがわかった。また、本反応も同様に、基質の適用範囲の拡大を目指し検討を行い、様々な二環式化合物の合成に利用可能であることも明らかにした。さらに、反応機構に関して詳細...
  • 文部科学省:科学研究費補助金(若手研究(B))
    研究期間 : 2008年 -2009年 
    代表者 : 大西 英博
     
    含窒素ヘテロ環カルベン(NHC)を配位子とするRh(I)錯体を合成し、実際に4-アルケナールのヒドロアシル化反応に適用した。その結果、NHCは有機リン配位子と同様にヒドロアシル化反応を進行させることが明らかになった。また、Rh(I)-NHC錯体と側鎖にアルキンを持つアレニルアルデヒドとの反応を検討したところ、ヒドロアシル化及びアルキンの挿入反応により生成したと考えられる二環式化合物が良好な収率で得られることを見出した。さらに、本反応を検討中にアレニルアルデヒドの分子内ヒドロアシル化反応の開発にも成功した。

教育活動情報

主要な担当授業

  • 大学院共通授業科目(一般科目):自然科学・応用科学
    開講年度 : 2021年
    課程区分 : 修士課程
    開講学部 : 大学院共通科目
    キーワード : transition metal catalysis, asymmetric catalysis, metallacycle, metathesis, carboxylation, synthesis of biologically active compounds
  • 先端有機金属化学特論
    開講年度 : 2021年
    課程区分 : 修士課程
    開講学部 : 生命科学院
    キーワード : transition metal catalysis, asymmetric catalysis, metallacycle, metathesis, carboxylation, synthesis of biologically active compounds
  • 化学Ⅱ
    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 : 有機化合物、官能基、分子構造、化学的性質、化学反応、機能性有機物、生体関連有機物質
  • 有機化学実習Ⅰ
    開講年度 : 2021年
    課程区分 : 学士課程
    開講学部 : 薬学部
    キーワード : 有機化学実験,基本的操作,ガラス細工,蒸留,再結晶,混融試験,薄層クロマトグラフィー,レポート
  • 有機化学実習Ⅱ
    開講年度 : 2021年
    課程区分 : 学士課程
    開講学部 : 薬学部
    キーワード : 有機化学実験,基本的操作,ガラス細工,蒸留,再結晶,混融試験,薄層クロマトグラフィー,合成反応,レポート


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