Asymmetric aldol reaction via enolates catalyzed by late transition metal complexes

• Project/Area Number: 18550038
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Kochi University
• Principal Investigator: KIYOOKA Syun-ichi Kochi University, 教育研究部自然科学系, 教授 (00036584)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥720,000); Fiscal Year 2008: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2007: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2006: ¥1,300,000 (Direct Cost: ¥1,300,000)
• Keywords: 不斉反応 / 不斉アルドール反応 / 後周期遷移金属触媒 / キラルニ核Pt触媒 / 後期遷移金属触媒 / Ptエルート / Pdエノレート / Pdスパルテイン錯体 / Ptエノレート

Research Abstract

これまであまり成功例のなかった後期遷移金属触媒を用いる不斉アルドール反応の研究を行った。Pdにキラル配位子としてBINAPを持つ錯体を合成し、きわめて簡便な反応条件で有効な不斉アルドール反応を進行させることに成功した。キラル配位子としてスパルテインを用いることもできその反応の適応範囲を広げることができた。一方、シリルケテンアセタールを求核剤とする不斉アルドール反応をPtを用いて非常に高効率に達成した。Ptはキラル配位子BINAPをもつキラル2核錯体であった。

Research Products

• [Journal Article] (μ-Hydroxo)-platinum complex-catalyzed enantioselective aldol reaction of aldehydes with 1-methoxy-2-methyl-1-(trimethylsilyloxy)propene. (2008)
  • Author(s): S. -i. Kiyooka, S. Matsumoto, M. Kojima, K. Sakonaka, and H. Maeda.
  • Journal Title: Tetrahedron Lett. 49 Pages: 1589-1592
  • Peer Reviewed
• [Journal Article] (μ-Hydroxo)-platinum complex-catalyzed enantioselective aldol reaction (2008)
  • Author(s): Kiyooka, S.-i.
  • Journal Title: Tetrahedron Letters 49 Pages: 1589-1592
  • Peer Reviewed
• [Journal Article] [IrCl(cod)]2-catalyzed direct oxidative esterfication (2007)
  • Author(s): Kiyooka, S.-i.
  • Journal Title: Tetrahedron 63 Pages: 12695-12701
  • Peer Reviewed
• [Journal Article] Dicationic ((-)-sparteine)-palladium-catalyzed enantioselective aldol reaction of aldehydes with 1-phenyl-1-trimethylsiloxyethene, proceeding via a palladium enolate (2006)
  • Author(s): S. -i. Kiyooka, Y. Takeshita, Y. Tanaka, T. Higaki, and Y. Wada.
  • Journal Title: Tetrahedron Lett. 47 Pages: 4453-4456
  • Peer Reviewed
• [Journal Article] Dicationic (BINAP)-palladium-catalyzed enantioselective aldol reaction of aldehydes with a silyl enol ether : a simplified practical procedure (2006)
  • Author(s): S. -i. Kiyooka, S. Hosokawa, and S. Tsukasa.
  • Journal Title: Tetrahedron Lett. 47 Pages: 3959-3962
  • Peer Reviewed
• [Journal Article] Dicationic ((-)-sparteine)palladium-catalyzed enantioselective aldol reaction (2006)
  • Author(s): Kiyooka, S. -i.
  • Journal Title: Tetrahedron Letters 47 Pages: 4453-4456
• [Journal Article] Dicationic (BINAP)palladium-catalyzed enantioselective aldol reaction (2006)
  • Author(s): Kiyooka, S. -i.
  • Journal Title: Tetrahedron Letters 47 Pages: 4453-4456
• [Presentation] (μ-Hydroxo)-platinum complex-catalyzed enantioselective aldol reaction for anti-propionates (2008)
  • Author(s): 清岡 俊一
  • Organizer: NINTH TETRAHEDRON SYMPOSIUM
  • Place of Presentation: Berkeley, CA, USA
  • Year and Date: 2008-07-23
• [Presentation] (μ-Hydroxo)-platinum complex-catalyzed enantioselective aldol reaction for anti-propionate (2008)
  • Author(s): S. -i. Kiyooka
  • Organizer: NINTH TETRAHEDRON SYMPOSIUM
  • Place of Presentation: Berkeley, CA, USA
• [Presentation] Chiral dicationic platinum-catalyzed enantioselective aldol reaction (2006)
  • Author(s): S. -i. Kiyooka
  • Organizer: SEVENTH TETRAHEDRON SYMPOSIUM
  • Place of Presentation: Kyoto, JAPAN