Reductive Construction of Carbon Skeleton with Newly Designed Asymmetric Catalysts

• Project/Area Number: 18350049
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Nagoya University
• Principal Investigator: NISHIYAMA Hisao Nagoya University, 工学研究科, 教授 (40135421)
• Project Period (FY): 2006 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥17,400,000 (Direct Cost: ¥15,600,000、Indirect Cost: ¥1,800,000); Fiscal Year 2009: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2008: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2007: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2006: ¥9,600,000 (Direct Cost: ¥9,600,000)
• Keywords: 不斉合成 / 反応 / ロジウム / 有機金属 / 配位子 / 炭素結合形成 / 炭素炭素結合生成 / 不斉触媒 / オキサゾリン

Research Abstract

New synthetic method of carbon skeletons and functional transformation has been examined with designed transition metal species, which has chiral oxazoline ligands. Via intermediates activated by silane or hydrogen, coupling reaction of esters or enones with aldehydes was promoted to form optically active compounds with diastereo- and enantio-selectivities.

Research Products

• [Journal Article] Intermolecular Antiselective and Enantioselective Reductive Coupling of Enones and Aromatic Aldehydes with Chiral Rh(Phebox) Catalysts (2009)
  • Author(s): T.Shiomi, T.Adachi, J.Ito, H.Nishiyama
  • Journal Title: Org.Lett. 11 Pages: 1011-1014
  • Peer Reviewed
• [Journal Article] Intermolecular Antiselective and Enantioselective Reductive Coupling of Enones and Aromatic Aldehydes with Chiral Rh(Phebox) Catalysts (2009)
  • Author(s): T.Shiomi, T.Adachi, J.Ito, H.Nishiyama
  • Journal Title: Org.Lett. Volume: 11 Pages: 1011-1014
  • Peer Reviewed
• [Journal Article] Catalytic Hydrosilylation of Carbonyl Compounds with Zinc(II) Acetate : Asy mmetric Induction Collaborated with N2S2 Ligands (2009)
  • Author(s): Inagaki, T., Nishiyamam H., et al.
  • Journal Title: Synlett ￣ Pages: 257-259
  • Peer Reviewed
• [Journal Article] Catalytic Hydrosilylation of Carbonyl Compounds with Zinc(II) Acetate : Asymmetric Induction Collaborated with N2S2 Ligands (2008)
  • Author(s): T.Inagaki, Y.Yamada, L.T.Phong, A.Furuta, J.Ito, H.Nishiyama
  • Journal Title: Synlett Pages: 257-259
  • Peer Reviewed
• [Journal Article] Catalytic Hydrosilylation of Carbonyl Compounds with Zinc(II) Acetate (2008)
  • Author(s): T. Inagaki, Y. Yamada, L. T. Phong, A. Furuta, J. Ito, H. Nishiyama
  • Journal Title: Asymmetric Induction Collaborated with N2S2 Ligands, Synlett Pages: 257-259
  • Peer Reviewed
• [Journal Article] Asymmetric Ligand Exchange Reaction on Biphenol Derivatives and Chiral Bis(oxazolinyl)phenyl-Rhodium Complex (2008)
  • Author(s): Inoue, H., Nishiyama, H., et al.
  • Journal Title: Chem. Asian J. 3 Pages: 1284-1288
  • Peer Reviewed
• [Journal Article] Highly Efficient Catalytic System for Hydrosilylation of ketones with lron (II) Acetate-Thiophenecarboxylate (2008)
  • Author(s): Furuta, A.; Nishiyama, H.
  • Journal Title: Tetrahedron Letters 49 Pages: 110-113
  • Peer Reviewed
• [Journal Article] Cross-Coupling of Alkynes Catalyzed by Phebox-rhodium Acetate Complexes (2007)
  • Author(s): J.Ito, M.Kitase, H.Nishiyama
  • Journal Title: Organometallics 26 Pages: 6412-6417
  • Peer Reviewed
• [Journal Article] Asymmetric Synthesis of α Chiral Dihydrocinnamates by Catalytic Reductive Aldol Coupling and Subsequent Dehydroxylation (2007)
  • Author(s): T.Hashimoto, T.Shiomi, J.Ito, H.Nishiyama
  • Journal Title: Tetrahedron 63 Pages: 12883-12887
  • Peer Reviewed
• [Journal Article] Diastereoselective reductive Mannich- type coupling of acrylates and aldimines with Rh(Phebox) catalyst (2007)
  • Author(s): H.Nishiyama, J.Ishikawa, T.Shiomi
  • Journal Title: Tetrahedron Lett. 48 Pages: 7841-7844
  • Peer Reviewed
• [Journal Article] Asymmetric Synthesis of α-Chiral Dihydrocinnamates by Catalytic Reductive Aldol Coupling and Subsequent Dehydroxylation (2007)
  • Author(s): T. Hashimoto, T. Shiomi, J. Ito, H. Nishiyama
  • Journal Title: Tetrahedron 63 Pages: 12883-12887
  • Peer Reviewed
• [Journal Article] Cross-Coupling of Alkynes Catalyzed by Phebox-rhodium Acetate Complexes (2007)
  • Author(s): J. Ito, M. Kitase, H. Nishiyama
  • Journal Title: Organometallics 26 Pages: 6412-6417
  • Peer Reviewed
• [Journal Article] Cross-Coupling of Alkynes Catalyzed by Phebox-rhodium Acetate Complexes (2007)
  • Author(s): Ito, J.; Kitase, M.; Nishiyama, H.
  • Journal Title: Organometallics 26 Pages: 6412-6417
  • Peer Reviewed
• [Journal Article] Synthesis and use of bisoxazolinyl-phenyl pincers (2007)
  • Author(s): Nishiyama, H.
  • Journal Title: Chem. Soc. Rev. (印刷中)
• [Journal Article] Carbon-Hydrogen Bond Activation of Arenes by (Phebox)Rh(III)-Acetate Complex (2007)
  • Author(s): Ito, J., Nishiyama, H.
  • Journal Title: Eur. J. Inorg. Chem. Pages: 1114-1119
• [Journal Article] Conjugate Reduction of β Unsaturated Aldehydes with Rhodium (bisoxazolinylphenyl) Catalysts (2006)
  • Author(s): K.Kanazawa, H.Nishiyama
  • Journal Title: Synlett Pages: 3343-3345
  • Peer Reviewed
• [Journal Article] Conjugate Reduction of α, β-Unsaturated Aldehydes with Rhodium (bisoxazolinylphenyl) (2006)
  • Author(s): K. Kanazawa, H. Nishiyama
  • Journal Title: Catalysts, Synlett Pages: 3343-3345
  • Peer Reviewed
• [Journal Article] A Carbon-Carbon Bond Formation on Bis(oxazolinyl)phenyl-Rhodium Complex in Reduction and Oxidative Addition Sequence (2006)
  • Author(s): Ito, J., Miyakawa, T., Nishiyama, H.
  • Journal Title: Organometallics 25 Pages: 5216-5218
• [Presentation] NCNピンサー型イリジウムアセテート錯体による炭素一炭素結合の活性化 (2009)
  • Author(s): 金田智子、伊藤淳一、西山久雄
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 同志社大学
  • Year and Date: 2009-09-11
• [Presentation] Rh(Phebox)触媒を用いるエノン類の不斉還元的アルドールカップリング (2009)
  • Author(s): 足立隆浩、塩見拓史、伊藤淳一、西山久雄
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2009-03-29
• [Presentation] 8, 9族遷移金属からなるNCNピンサー型錯体の合成と反応 (2009)
  • Author(s): 伊藤淳一、宮川剛志、氏家諭史、北瀬恵、細川さとみ、西山久雄
  • Organizer: 第55回有機金属化学討論会
• [Presentation] Rh(Phebox)アセテート錯体によるアルキン類の活性化 (2009)
  • Author(s): 北瀬恵、伊藤淳一、西山久雄
  • Organizer: 日本化学会第88回春季年会
• [Presentation] 8,9族遷移金属からなるNCNピンサー型錯体の合成と反応 (2008)
  • Author(s): 伊藤淳一、宮川剛志、氏家諭史、北瀬恵、細川さとみ、西山久雄
  • Organizer: 第55回有機金属化学討論会
  • Place of Presentation: 大阪府立大学
  • Year and Date: 2008-09-29
• [Presentation] Phebox-Rh Acetate Complex Catalyzed Cross-Coupling of Alkynes (2008)
  • Author(s): 北瀬恵、伊藤淳一、西山久雄
  • Organizer: ICOMC2008
  • Place of Presentation: University of Rennes, France
  • Year and Date: 2008-07-14
• [Presentation] Asymmetric Reductive Aldol Coupling with Bisoxazolinylphenyl-Rhodium Complexes (2008)
  • Author(s): 西山久雄、橋本徹、足立隆浩、塩見拓史
  • Organizer: ICOMC2008
  • Place of Presentation: University of Rennes, France
  • Year and Date: 2008-07-14
• [Presentation] Rh-Phebox触媒を用いた還元アルドール反応による三連続不斉炭素を有するβ-ヒドロキシエステルの立体制御 (2008)
  • Author(s): 橋本徹、西山久雄
  • Organizer: 日本化学会第88回春季年会
  • Place of Presentation: 立教大学
  • Year and Date: 2008-03-30
• [Presentation] Rh-Phebox触媒を用いたアンチ選択的還元マンニッヒ反応 (2008)
  • Author(s): 石川準二、塩見拓史、西山久雄
  • Organizer: 日本化学会第88回春季年会
  • Place of Presentation: 立教大学
  • Year and Date: 2008-03-30
• [Presentation] Rh(Phebox)アセテート錯体によるアルキン類の活性化 (2008)
  • Author(s): 北瀬恵、伊藤淳一、西山久雄
  • Organizer: 日本化学会第88回春季年会
  • Place of Presentation: 立教大学
  • Year and Date: 2008-03-28
• [Presentation] 光学活性ロジウム錯体を用いた触媒的不斉アルドール反応 (2008)
  • Author(s): 菊池淳、井上寛子、西山久雄
  • Organizer: 日本化学会第87回春季年会
• [Presentation] 光学活性ロジウム錯体を用いた触媒的不斉アルドール反応 (2007)
  • Author(s): 菊池淳、井上寛子、西山久雄
  • Organizer: 日本化学会第87回春季年会
  • Place of Presentation: 立教大学
  • Year and Date: 2007-03-27
• [Book] Top. Curr. Chem.: Metal Catalyzed Reductive C-C Bond Formation (2007)
  • Author(s): H. Nishiyama, T. Shiomi, Reductive Aldol, Michael and Mannich Reactions
  • Publisher: Ed. M. J. Krische, Springer-Verlag, Berlin
• [Book] Top.Curr.Chem.: Metal Catalyzed Reductive C-C Bond Formation(Ed.M.J.Krische)
  • Author(s): H.Nishiyama, T.Shiomi, Reductive Aldol, Michael, Mannich Reactions
  • Publisher: Springer-Verlag, Berlin