Development of Chirally Flexible Catalysts in Asymmetric Activation

• Project/Area Number: 17350045
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: MIKAMI Koichi Tokyo Institute of Technology, 大学院・理工学研究科, 教授 (10157448)
• Project Period (FY): 2005 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥16,860,000 (Direct Cost: ¥14,700,000、Indirect Cost: ¥2,160,000); Fiscal Year 2008: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2007: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2006: ¥3,600,000 (Direct Cost: ¥3,600,000); Fiscal Year 2005: ¥3,900,000 (Direct Cost: ¥3,900,000)
• Keywords: キラル / 不斉合成 / 不斉活性化 / 動的キラル / 光学分割 / ラセミ配位子 / 触媒的不斉合成 / BIPHEP / 軸不斉 / 不斉制御 / 不斉記憶 / chirality / ベンゾフェノン / BINAP / 炭素-炭素結合生成 / 不斉水素化反応 / Ru錯体 / 遷移金属錯体 / DPEN / 水素移動型不斉還元 / 不斉

Research Abstract

Pd カチオン錯体触媒をはじめとする後周期遷移金属Pt、Ni、Rh、Ir、Ru錯体あるいは前周期遷移金属Ti、Zr 錯体の「動的キラル」な配位子の「不斉活性化」に基づくキラル制御を行った.得られた光学的に純粋な「動的キラル」な錯体触媒をもとに、不斉触媒的炭素-炭素結合生成反応の開発を行った.更にその成果をもとに、生理活性物質の効率的な触媒的不斉合成反応を行なった.

Research Products

• [Journal Article] Instant Chirality Control in Diphenylmethane-based Phosphoramidite Ligands : Highly Enantioselective Conjugate Addition to Nitroalkenes and Nitroacrylates (2008)
  • Author(s): Kazuki Wakabayashi, Kohsuke Aikawa, Susumu Kawauchi, Koichi Mikami
  • Journal Title: J. Am. Chem. Soc 130(15) Pages: 5012-5013
  • Peer Reviewed
• [Journal Article] Benzophenone-derived Catalysts with Self-adaptation : Highly Enantioselective Hydrogenation Irrespective of Substrates (2008)
  • Author(s): Kazuki Wakabayashi, Kohsuke Aikawa, Koichi Mikami
  • Journal Title: Heterocycles 76 Pages: 1525-1535
  • Peer Reviewed
• [Journal Article] Axial Chirality Control of Tropos BIPHEPs-Rh Complexes by Chiral Dienes : Synergy Effect in Catalytic Asymmetric Hydrogenation (2008)
  • Author(s): Kohsuke Aikawa, Yuki Takabayashi, Susumu Kawauchi, Koichi Mikami
  • Journal Title: Chem. Comm Pages: 5095-5097
  • Peer Reviewed
• [Journal Article] Axial Chirality Control of Tropos BIPHEPs-Rh Complexes by Chiral Dienes : Synergy Effect in Catalytic Asymmetric Hydrogenation (2008)
  • Author(s): Aikawa, K., Takabayashi, Y, Kawauchi, S., Mikami, K.
  • Journal Title: Chemical Communications Pages: 5095-5097
  • Peer Reviewed
• [Journal Article] Benzophenone-derived Catalysts with Self-adaptation : Highly Enantioselective Hydrogenation Irrespective of Substrates (2008)
  • Author(s): Wakabayashi, K., Aikawa, K., Mikami, K.
  • Journal Title: Heterocycles 76 Pages: 1525-1535
  • Peer Reviewed
• [Journal Article] Instant Chirality Control in Diphenylmethane-based Phosphoramidite Ligands : Highly Enantioselective Conjugate Addition io Nitroalkenes and Nitroacrylates (2008)
  • Author(s): Wakabayashi, K., Aikawa, K., Kawauchi, S., Mikami, K.
  • Journal Title: Journal of the American Chemical Society 130 Pages: 5012-5013
  • Peer Reviewed
• [Journal Article] Catalyst Self-Adaptation in Conjugate Addition to Nitroalkenes and Nitoacrylates:Instant Chirality Control in Diphenylmethane-Based Phosphoramidite Ligands (2008)
  • Author(s): 若林一樹、相川光介、川内進、三上幸一
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 5012-5013
  • Peer Reviewed
• [Journal Article] Enantiofacial Control of Planar Chiral Arene Ru Complexes Bearing Tropos Biphenyl Ligands (2007)
  • Author(s): Kohsuke Aikawa, Isao Kaito, Koichi Mikami
  • Journal Title: Chem. Lett 36(12) Pages: 1482-1483
  • NAID: 10020012195
  • Peer Reviewed
• [Journal Article] Enantiofacial Control of Planar Chiral Arene Ru Complexes Bearing Tropos Biphenyl Ligands (2007)
  • Author(s): 相川光介、海藤功、三上幸一
  • Journal Title: Chemistry Letters 36 Pages: 1482-1483
  • NAID: 10020012195
  • Peer Reviewed
• [Journal Article] Chiral Aminoalcohol NOBIN for Instantaneous Chirality Control of Racemic but Tropos BIPHEP-Rh(I)-Complexes : Highly Enantioselective Ene-Type Cyclization of 1, 6-Enynes Catalyzed by the Rh(I)-Complexes without Use of Acid (2006)
  • Author(s): Koichi Mikami, Shohei Kataoka, Kazuki Wakabayashi, Kohsuke Aikawa
  • Journal Title: Tetrahedron Lett 47 Pages: 6361-6364
  • Peer Reviewed
• [Journal Article] Achiral benzophenone ligand-rhodium complex with chiral diamine activator for high enantiocontrol in asymmetric transfer hydrogenation (2006)
  • Author(s): Koichi Mikami, Kazuki Wakabayashi, Kohsuke Aikawa
  • Journal Title: Chem. Commun Pages: 2365-2367
  • Peer Reviewed
• [Journal Article] Achiral Benzophenone Ligand for Highly Enantioselective Ru Catalysts in Ketone Hydrogenation (2006)
  • Author(s): Koichi Mikami, Kazuki Wakabayashi, Kohsuke Aikawa
  • Journal Title: Org. Lett 8 Pages: 1517-1519
  • Peer Reviewed
• [Journal Article] "Achiral" Benzophenone Ligand for Highly Enantioselective Ru-Catalysts in Ketone Hydrogenation (2006)
  • Author(s): Mikami, K., Wakabayashi, K., Aikawa, K.
  • Journal Title: Organic Letter 8 Pages: 1517-1519
• [Journal Article] Chiral Aminoalcohol NOBIN for Instantaneous Chirality Control of Racemic but Tropos BIPHEP-Rh(I)-Complexes : Highly Enantioselective Ene-Type Cyclization of 1,6-Enynes Catalyzed by Rh(I)-Complexes without Use of Acid (2006)
  • Author(s): Mikami, K., Kataoka, S., Wakabayashi, K., Aikawa, K.
  • Journal Title: Tetrahedron Lettetrs 47 Pages: 6361-6364
• [Journal Article] Achiral Benzophenone Ligand-Rhodium Complex with Chiral Diamine Activator for High Enantiocontrol in Asymmetric Transfer Hydrogenation (2006)
  • Author(s): Mikami, K., Wakabayashi, K., Yusa, Y., Aikawa, K.
  • Journal Title: Chem. Comm. 22 Pages: 2365-2367
• [Journal Article] Achiral Benzophenone Ligand for Highly Enantioselective Ru Catalysts in Ketone Hydrogenation (2006)
  • Author(s): Koichi Mikami, Kazuki Wakabayashi, Kohsuke Aikawa
  • Journal Title: Org.Lett. 8(in press)
• [Journal Article] Achiral Benzophenone Ligand with Chiral Diamine Activator for High Enantiocontrol (2006)
  • Author(s): Koichi Mikami, Kazuki Wakabayashi, Kohsuke Aikawa
  • Journal Title: Chem.Commun 47(in press)
• [Journal Article] Enantio-Discrimination and -Control of Neutral and Cationic Pt(II) Complexes Bearing Tropos BIPHEP Ligand : Its Application to Asymmetric Lewis Acid Catalysis (2005)
  • Author(s): Koichi Mikami, Hitomi Kakuno, Kohsuke Aikawa
  • Journal Title: Angew. Chem. Int. Ed 44 Pages: 7257-7260
  • Peer Reviewed
• [Journal Article] Dual Chirality Control of Palladium(II) Complexes Bearing Tropos Biphenyl Diamine Ligands (2005)
  • Author(s): Kohsuke Aikawa, Koichi Mikami
  • Journal Title: Chem. Commun Pages: 5799-5801
  • Peer Reviewed
• [Journal Article] Tropos or Atropos Nature of Rh(I) Complexes Bearing aTetrakis(phosphanyl)terphenyl (TETRAPHOS) Ligand : Highly Enantioselective Catalysis of Ene-type Cyclization (2005)
  • Author(s): Koichi Mikami, Shohei Kataoka, Kohsuke Aikawa
  • Journal Title: Org. Lett 7 Pages: 5777-5780
  • Peer Reviewed
• [Journal Article] Theoretical Study on the Tropos Nature of the BIPHEP-Pd(II)/DABN and /DPEN Complexes : PIO Analysis of Phosphine-Pd(II) Interaction and Trans Influence (2005)
  • Author(s): Masahiro Yamanaka, Koichi Mikami
  • Journal Title: Organometallics 24 Pages: 4579-4587
  • Peer Reviewed
• [Journal Article] Dual Chirality Control of Palladium(II) Complexes Bearing Tropos Biphenyl Diamine Ligands (2005)
  • Author(s): Kohsuke Aikawa, Koichi Mikami
  • Journal Title: Chem.Commun. 46 Pages: 5799-5801
• [Journal Article] Enantio-Discrimination and-Control of Neutral and Cationic Pt(II) Complexes Bearing Tropos BIPHEP Ligand : Its Application to Asymmetric Lewis Acid Catalysis (2005)
  • Author(s): Koichi Mikami, Hitomi Kakuno, Kohsuke Aikawa
  • Journal Title: Angew.Chem.Int.Ed. 44 Pages: 7257-7260
• [Journal Article] Tropos or Atropos Nature of Rh(I) Complexes Bearing a Tetrakis(phosphanyl)terphenyl (TETRAPHOS) Ligand : Highly Enantioselective Catalysis of Ene-type Cyclization (2005)
  • Author(s): Koichi Mikami Shohei Kataoka, Kohsuke Aikawa
  • Journal Title: Org.Lett. 7 Pages: 5777-5780
• [Journal Article] Theoretical Study on the Tropos Nature of the BIPHEP-Pd(II)/DABN and/DEPN Complexes : PIO Analysis of Phosphine-Pd(II) Interaction and Trans Influence (2005)
  • Author(s): Masahiro Yamanaka, Koichi Mikami
  • Journal Title: Organometallics 24 Pages: 4579-4587
• [Presentation] ホスフィン- Rh-ジエン錯体の熱力学的・速度論的不斉制御とその不斉触媒反応 (2008)
  • Author(s): 若林一樹、相川光介、三上幸一
  • Organizer: 第93回有機合成シンポジウム
  • Place of Presentation: 東京工業大学
  • Year and Date: 2008-06-13
• [Presentation] ホスフインーRh-ジェン錯体の熱力学的・速度論的不斉制御とその不斉触媒反応 (2008)
  • Author(s): 若林 一樹
  • Organizer: 第93回有機合成シンポジウム
  • Place of Presentation: 東京工業大学
  • Year and Date: 2008-06-13
• [Presentation] ベンゾフェノンを基本骨格としたphosphoramidite 配位子の迅速な不斉制御と高エナンチオ選択的不斉触媒反応への活用 (2008)
  • Author(s): 若林一樹、相川光介、三上幸一
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 立教大学
  • Year and Date: 2008-03-27
• [Presentation] ベンゾフェノンを基本骨格としたphosphoramidite配位子の迅速な不斉制御と高エナンチオ選択的不斉触媒反応への活用 (2008)
  • Author(s): 若林一樹、相川光介、三上幸一
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 立教大学
  • Year and Date: 2008-03-27
• [Book] New Frontier in Asymmetric Catalsis ; Mikami, K., Loutens, M., Eds. ; WILEY : New York (2007)
  • Author(s): Koichi Mikami, Kohsuke Aikawa
  • Publisher: Asymmetric Activation and Deactivation of Racemic Catalysts
• [Book] New Frontiers in Asymmetric Catalysis (2007)
  • Author(s): 三上幸一、相川光介
  • Total Pages: 418
  • Publisher: WILEY
• [Book] New Frontier in Asymmetric Catalsis (2007)
  • Author(s): Mikami, K., Loutens, M.
  • Publisher: WILEY-VCH (in press)
• [Book] In New Frontier in Asymmetric Catalysis (2006)
  • Author(s): Koichi Mikami, Kohsuke Aikawa
  • Publisher: Wiley-VCH(in press)
• [Remarks]
  • URL: http://www.apc.titech.ac.jp/%7Emikami/index-j.html
• [Remarks]
  • URL: http://www.apc.titech.ac.jp/%7Emikami/index-j.html