Development of new activators for trichlorosilane

• Project/Area Number: 19550109
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Nagasaki University
• Principal Investigator: ONOMURA Osamu Nagasaki University, 大学院・医歯薬学総合研究科, 教授 (60304961)
• Project Period (FY): 2007 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2008: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2007: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
• Keywords: 不斉合成 / 不斉還元 / 有機触媒 / アルコール / アミン / 活性化剤 / トリクロロシラン / 高配位ケイ素 / プロリン / 光学活性アルコール / 光学活性アミン / ジアステレオ選択性 / エナンチオ選択性

Research Abstract

トリクロロシランは太陽電池や半導体に使用される高純度シリコンの原料として入手容易である。これを用いてケトンやイミンを不斉還元し、医薬品等の中間体として有用な光学活性アルコールやアミンを合成するためにはトリクロロシランを効率的に活性化する触媒が必要である。本研究課題では、L-プロリンからケトンやイミンの高効率不斉還元に適した有機触媒を開発することに成功した。その結果、有用なこれら光学活性化合物を環境に調和した反応によって得られるようになった。

Research Products

• [Journal Article] Efficient oxidation of 1,2-diols into □-hydroxyketones catalyzed by organotin compound (2009)
  • Author(s): T. Maki, S. Iikawa, G. Mogami, H. Harasawa, Y. Matsumura, and O. Onomura
  • Journal Title: Chem. Eur. J. (in press)
  • Peer Reviewed
• [Journal Article] Catalytic monoalkylation of 1,2-diols (2009)
  • Author(s): T. Maki, N. Ushijima, Y. Matsumura and O. Onomura
  • Journal Title: Tetrahedron Lett. 50 Pages: 1466-1468
  • NAID: 120006983324
  • Peer Reviewed
• [Journal Article] Memory of Chirality in the Electrochemical Oxidation of N-o-Phenylbenzoylated Prolinols (2009)
  • Author(s): G. N. Wanyoike, Y. Matsumura, and O. Onomura
  • Journal Title: Heterocycles (Daly追悼号) (in press)
  • NAID: 120006984131
  • Peer Reviewed
• [Journal Article] Ring Contraction of α, β-Unsaturated CyclicAmines with cis-Dihydroxylation at theα, β-Position (2009)
  • Author(s): S. S. Libendi, Y. Demizu, Y. Matsumura, and O. Onomura
  • Journal Title: Heterocycles(福本祝賀号) 77 Pages: 311-321
  • Peer Reviewed
• [Journal Article] Direct Electrochemical α-Cyanation of N-Protected Cyclic Amines (2009)
  • Author(s): Osamu Onomura
  • Journal Title: Ore. & Biomol. Chem 7 Pages: 351-356
  • Peer Reviewed
• [Journal Article] Ring Contraction of α, β-Unsaturated Cyclic Amines with cis-Dihydroxylation at the α, β-Position (2009)
  • Author(s): Osamu Onomura
  • Journal Title: Heterocycles 77 Pages: 311-321
  • NAID: 120006984130
  • Peer Reviewed
• [Journal Article] Convenient synthesis of enantiomerically pure bicyclic proline and its N-oxyl derivatives (2008)
  • Author(s): Yosuke Demizu, Hirofumi Shiigi, Hiroyuki Mori, Kazuya Matsumoto and Osamu Onomura
  • Journal Title: Tetrahedron : Asymmetry 19 Pages: 2659-2665
  • NAID: 120006983370
  • Peer Reviewed
• [Journal Article] D. Minato, Y. Nagasue, Y. Demizu, and O. Onomura (2008)
  • Author(s): Effecient Kinetic Resolution of racemic-Aminoaldehydes by Oxidation with NIS
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 9458-9461
  • Peer Reviewed
• [Journal Article] Regioselective Protection of Sugars Catalyzed by Dimethyltin Dichloride (2008)
  • Author(s): Y. Demizu, Y. Kubo, H. Miyoshi, T. Maki, Y. Matsumura, N. Moriyama, and O. Onomura
  • Journal Title: Org. Lett. 10 Pages: 5075-5077
  • Peer Reviewed
• [Journal Article] Oxidative C-C bond cleavage of N-alkoxycarbonylated cyclic amines by sodium nitrite in trifluoroacetic acid (2008)
  • Author(s): O. Onomura, A. Moriyama, K. Fukae, Y. Yamamoto, T. Maki, Y. Matsumura, and Y. Demizu
  • Journal Title: Tetrahedron Lett. 49 Pages: 6728-6731
  • NAID: 120006982372
  • Peer Reviewed
• [Journal Article] Asymmetric reductions of [m] ferrocenophanones (2008)
  • Author(s): R. Sebesta, M. Meciarova, E. Molnar, J. Czismadiova, P. Fodran, O. Onomura, and-. Toma, J
  • Journal Title: Organomet. Chem. 693 Pages: 3131-3134
  • Peer Reviewed
• [Journal Article] Regioselective introduction of electrophiles into piperidine derivatives at the 4-position (2008)
  • Author(s): O. Onomura, N. Fujimura, T. Oda, Y. Matsumura, and Y. Demizu
  • Journal Title: Heterocycles(野依祝賀号) 76 Pages: 177-182
  • NAID: 120006984129
  • Peer Reviewed
• [Journal Article] Chiral azabicyclo-N-oxyls mediated enantioselective electrooxidation of secalcohols (2008)
  • Author(s): H. Shiigi, H. Mori, T. Tanaka, Y. Demizu and O. Onomura
  • Journal Title: Tetrahedron Lett. 49 Pages: 5247-5251
  • NAID: 120006981658
  • Peer Reviewed
• [Journal Article] Diastereoselective arylation of L-proline derivatives at the 5-position (2008)
  • Author(s): O. Onomura, P. G. Kirira, T. Tanaka, S. Tsukada, Y. Matsumura, Y. Demizu
  • Journal Title: Tetrahedron 64 Pages: 7498-7503
  • NAID: 120006981712
  • Peer Reviewed
• [Journal Article] Asymmetric electrochemical oxidation of 1,2-diols, aminoalcohols, and aminoaldehydes in the presence of chiral copper catalyst (2008)
  • Author(s): D. Minato, H. Arimoto, Y. Nagasue, Y. Demizu, and Osamu Onomura
  • Journal Title: Tetrahedron 64 Pages: 6675-6683
  • NAID: 120006981074
  • Peer Reviewed
• [Journal Article] High regioselectivity in electrochemical α-methoxylation of N-protected cyclic amines (2008)
  • Author(s): S. S. Libendi, Y. Demizu, Y.Matsumura, and O. Onomura
  • Journal Title: Tetrahedron 64 Pages: 3935-3942
  • NAID: 120006981389
  • Peer Reviewed
• [Journal Article] Non-enzymatic kinetic resolution of 3-hydroxyalkanamides with chiral copper catalyst (2008)
  • Author(s): Y. Demizu, Y. Kubo, Y. Matsumura, and O. Onomura
  • Journal Title: Synlett Pages: 433-437
  • NAID: 120006982422
  • Peer Reviewed
• [Journal Article] Efficient oxidation of alcohols electrochemically mediated by azabicyclo-Noxyls (2008)
  • Author(s): Y. Demizu, H. Shiigi, T. Oda, Y. Matsumura and O. Onomura
  • Journal Title: Tetrahedron Lett. 49 Pages: 48-52
  • NAID: 120006981360
  • Peer Reviewed
• [Journal Article] Convenient synthesis of enantiomerically pure bicyclic proline and its N-oxyl derivatives (2008)
  • Author(s): Osamu Onomura
  • Journal Title: Tetrahedron : Asymmetry 19 Pages: 2659-2665
  • NAID: 120006983370
  • Peer Reviewed
• [Journal Article] Effecient Kinetic Resolution of racemic-Aminoaldehydes by Oxidation with NIS (2008)
  • Author(s): Osamu Onomura
  • Journal Title: Angew. Chem. Int. Ed 47 Pages: 9458-9461
  • Peer Reviewed
• [Journal Article] Regioselective Protection of Sugars Catalyzed by Dimethyltin Dichloride (2008)
  • Author(s): Osamu Onomura
  • Journal Title: Org. Lett. 10 Pages: 5075-5077
  • Peer Reviewed
• [Journal Article] Oxidative C-C bond cleavage of N-alkoxycarbonylated cyclic amines by sodium nitrite in trifluoroacetic acid (2008)
  • Author(s): Osamu Onomura
  • Journal Title: Tetrahedron Lett. 49 Pages: 6228-6231
  • NAID: 120006982372
  • Peer Reviewed
• [Journal Article] Asymmetric reductions of[m]ferrocenophanones (2008)
  • Author(s): Osamu Onomura
  • Journal Title: J. Oreanomet. Chem. 693 Pages: 3131-3134
  • Peer Reviewed
• [Journal Article] Regioselective introduction of electrophiles into piperidine derivatives at the 4-position (2008)
  • Author(s): Osamu Onomura
  • Journal Title: Heterocvcles 76 Pages: 177-182
  • NAID: 120006984129
  • Peer Reviewed
• [Journal Article] Chiral azabicyclo-N-oxyls mediated enantioselective electrooxidation of sec-alcohols (2008)
  • Author(s): Osamu Onomura
  • Journal Title: Tetrahedron Lett. 49 Pages: 5247-5221
  • NAID: 120006981658
  • Peer Reviewed
• [Journal Article] Diastereoselective arylation of L-proline derivatives at the 5-position (2008)
  • Author(s): Osamu Onomura
  • Journal Title: Tetrahedron 64 Pages: 7498-7503
  • NAID: 120006981712
  • Peer Reviewed
• [Journal Article] Asymmetric electrochemical oxidation of 1, 2-diols, aminoalcohols, and aminoaldehydes in the presence of chiral copper catalyst (2008)
  • Author(s): Osamu Onomura
  • Journal Title: Tetrahedron 64 Pages: 6675-6683
  • NAID: 120006981074
  • Peer Reviewed
• [Journal Article] High regioselectivity in electrochemical a-methoxylation of N-protected cyclic amines (2008)
  • Author(s): Osamu Onomura
  • Journal Title: Tetrahedron 64 Pages: 3935-3942
  • Peer Reviewed
• [Journal Article] Nonenzaymatic Kinetic Resolution of 3-Hydroxyalkanamides with Chiral Copper catalyst (2008)
  • Author(s): Y.Demizu
  • Journal Title: Synlett Pages: 433-437
  • Peer Reviewed
• [Journal Article] Asymmetric tosylation of racemic 2-hydroxyalkanamides with chiral copper catalyst (2007)
  • Author(s): O. Onomura, M. Mitsuda, M. T. T. Nguyen, and Y. Demizu
  • Journal Title: Tetrahedron Lett. 48 Pages: 9080-9084
  • NAID: 120006981361
  • Peer Reviewed
• [Journal Article] Asymmetric oxidation of 1,2-diols using N-bromosuccinimide in the presence of chiral copper catalyst (2007)
  • Author(s): O. Onomura, H. Arimoto, Y. Matsumura, and Y. Demizu
  • Journal Title: Tetrahedron Lett. 48 Pages: 8668-8672
  • NAID: 120006981362
  • Peer Reviewed
• [Journal Article] Copper complex catalyzed asymmetric monosulfonylation of meso-vic-diols (2007)
  • Author(s): Y. Demizu, K. Matsumoto, O. Onomura, and Y. Matsumura
  • Journal Title: Tetrahedron Lett. 48 Pages: 7605-7609
  • NAID: 120006981364
  • Peer Reviewed
• [Journal Article] トリクロロシランの触媒的活性化法の開発と還元反応への応用 (2007)
  • Author(s): 尾野村治、岩崎史哲
  • Journal Title: ファインケミカル 36(9) Pages: 37-43
• [Journal Article] トリクロロシランの触媒的活性化法の開発と還元反応への応用 (2007)
  • Author(s): 尾野 村治
  • Journal Title: ファインケミカル 36(9) Pages: 36-43
• [Journal Article] Asymmetric tosylation of racemic 2-hydroxyalkanamides with chiral copper catalyst (2007)
  • Author(s): O.Onomura
  • Journal Title: Tetrahedron Letters 48 Pages: 9080-9084
  • NAID: 120006981361
  • Peer Reviewed
• [Journal Article] Direct Electrochemical α-Cyanation of N-Protected Cyclic Amines
  • Author(s): S. S. Libendi, Y. Demizu, and O. Onomura
  • Journal Title: Org. & Biomol. Chem. 7 Pages: 351-356
  • Peer Reviewed
• [Presentation] Preparation of chiral quaternary cyclic aminoacids using anodic deallylation (2009)
  • Author(s): 尾野村治
  • Organizer: 電気化学会第76回大会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-31
• [Presentation] トリクロロシランの新規活性化剤の開発とイミンの不斉還元 (2008)
  • Author(s): 尾野村治
  • Organizer: 第24回日本薬学会九州支部大会
  • Place of Presentation: 福岡
  • Year and Date: 2008-12-08
• [Presentation] トリクロロシランによるイミンのシス選択的還元と速度論的光学分割 (2008)
  • Author(s): 尾野村治
  • Organizer: 第25回日本薬学会九州支部大会
  • Place of Presentation: 延岡
  • Year and Date: 2008-12-06
• [Presentation] The 9th International Symposium on Organic Reactions (2008)
  • Author(s): Osamu Onomura、Catalytic Activation of Trichlorosilane with Organocatalysts
  • Place of Presentation: 台湾、嘉義(招待講演)
  • Year and Date: 2008-11-22
• [Presentation] L-プロリン5位への立体選択的求核剤導入法の開拓 (2008)
  • Author(s): 尾野村治
  • Organizer: 第38回複素環化学討論会
  • Place of Presentation: 福山
  • Year and Date: 2008-11-22
• [Presentation] Catalytic Activation of Trichlorosilane with Organocatalysts、The 9th International Symposium on Organic Reactions (2008)
  • Author(s): 尾野村 治
  • Organizer: The 9th International Symposium on Organic Reactions
  • Place of Presentation: 嘉義、台湾
  • Year and Date: 2008-11-22
• [Presentation] 有機触媒によるトリクロロシランの触媒的活性化 (2008)
  • Author(s): 尾野村治
  • Organizer: 2008年日本化学会西日本大会
  • Place of Presentation: 長崎(依頼講演)
  • Year and Date: 2008-11-16
• [Presentation] 機触媒によるトリクロロシランの触媒的活性化 (2008)
  • Author(s): 尾野村 治
  • Organizer: 2008年日本化学会西日本大会
  • Place of Presentation: 長崎
  • Year and Date: 2008-11-16
• [Presentation] L-プロリン5位へのジアステレオ選択的アリール基導入とトリクロロシラン類のキラル活性化剤合成への利用 (2008)
  • Author(s): 尾野村治
  • Organizer: 第37回複素環化学討論会
  • Place of Presentation: 長野
  • Year and Date: 2008-10-19
• [Presentation] 不斉酸化を目指したジオール類の分子認識(招待講演) (2008)
  • Author(s): 尾野村治
  • Organizer: 第32回有機電子移動化学討論会
  • Place of Presentation: 東大阪
  • Year and Date: 2008-06-27
• [Presentation] 不斉酸化を目指したジオール類の分子認識 (2008)
  • Author(s): 尾野村 治
  • Organizer: 第32回有機電子移動化学討論会
  • Place of Presentation: 東大阪
  • Year and Date: 2008-06-26
• [Presentation] 環状アミン類の電極酸化を基盤とする精密有機合成 (2008)
  • Author(s): 尾野村治
  • Organizer: 電気化学会第75回大会
  • Place of Presentation: 甲府(特別講演).
  • Year and Date: 2008-03-31
• [Presentation] 簡単にできる不斉合成-ジオール類の分子変換(依頼講演) (2008)
  • Author(s): 尾野村治
  • Organizer: 薬学研究フォーラムin東京2008-九州からの情報発信
  • Place of Presentation: 東京
  • Year and Date: 2008-03-14
• [Presentation] トリクロロシランの新規活性化剤の開発とイミンの不斉還元 (2007)
  • Author(s): 尾野 村治, 他
  • Organizer: 日本薬学会九州支部大会
  • Place of Presentation: 福岡
  • Year and Date: 2007-12-08
• [Presentation] 光学活性C2対称ピロリジンの合成とその有機触媒としての利用 (2007)
  • Author(s): 尾野 村治, 他
  • Organizer: 2007プロセス化学会サマーシンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2007-08-03
• [Presentation] 光学活性C2対称ピロリジン誘導体の合成とその有機触媒としての利用 (2007)
  • Author(s): 尾野村治
  • Organizer: 日本プロセス化学会2007サマーシンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2007-08-02
• [Book] The Chemistry of Hydroxylamines, Oximes and Hydroxamic Acids Chapter 11. Electrochemistry of hydroxylamines, oximes and hydroxamic acids(John Wiley & Sons) (2008)
  • Author(s): O. Onomura
  • Publisher: Edited by Zvi Rappoport and Joel F. Liebman、Patai
• [Book] edited by Zvi Rappoport and Joel F. Liebman、Patai “The Chemistry of Hydroxylamines, Oximes and Hydroxamic Acids", “11. Electrochemistry of hydroxylamines, oximes and hydroxamic acids" (2008)
  • Author(s): Osamu Onomura
  • Publisher: John Wiely & Sons, Ltd.
• [Remarks]
  • URL: http://www.ph.nagasaki-u.ac.jp/lab/synchem/doc/paper-j.html
• [Remarks]
  • URL: http://www.ph.nagasaki-u.ac.jp/achievement/index.html
• [Patent(Industrial Property Rights)] 含窒素レドックス触媒 (2008)
  • Inventor(s): 松村功啓、出水庸介、尾野村治
  • Industrial Property Rights Holder: 長崎大学
  • Filing Date: 2008-03-28
  • Overseas
• [Patent(Industrial Property Rights)] 脂肪族ジカルボン酸化合物の製造方法 (2008)
  • Inventor(s): 尾野村治、出水庸介、岩崎史哲
  • Industrial Property Rights Holder: 長崎大学&(株)トクヤマ
  • Industrial Property Number: 2008-025594
  • Filing Date: 2008-02-05
• [Patent(Industrial Property Rights)] 光学活性アミノ酸エステル誘導体、及び光学活性アミノアセタール誘導体の製造方法 (2008)
  • Inventor(s): 尾野村治、出水庸介、山本博将
  • Industrial Property Rights Holder: 長崎大学&(株)トクヤマ
  • Industrial Property Number: 2008-072911
  • Filing Date: 2008-03-21
• [Patent(Industrial Property Rights)] α, α-ジ置換環状含窒素化合物の製造方法 (2007)
  • Inventor(s): 松村功啓、出水庸介、尾野村治
  • Industrial Property Rights Holder: 長崎大学
  • Industrial Property Number: 2007-084895
  • Filing Date: 2007-03-28
• [Patent(Industrial Property Rights)] 光学活性プロリンエステル誘導体およびN-ホルミル光学活性プロリン誘導体の製造方法 (2007)
  • Inventor(s): 尾野村治、岩崎史哲
  • Industrial Property Rights Holder: 長崎大学&(株)トクヤマ
  • Industrial Property Number: 2007-205118
  • Filing Date: 2007-08-07
• [Patent(Industrial Property Rights)] 光学活性プロリン誘導体およびN-ホルミル光学活性プロリン誘導体の製造方法 (2007)
  • Inventor(s): 尾野 村治・ 岩崎 史哲
  • Industrial Property Rights Holder: 長崎大・(株)トクヤマ
  • Industrial Property Number: 2007-205118
  • Filing Date: 2007-08-07