Asymmetric Cyanation and Hydrogenation Catalyzed by Ruthenium Complexes

2014 Fiscal Year Final Research Report

• Project/Area Number: 24350042
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: OHKUMA Takeshi 北海道大学, 工学(系)研究科(研究院), 教授 (50201968)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Keywords: 触媒的不斉合成 / 不斉シアノ化反応 / 不斉水素化反応 / ケトン / イミン / シアン化化合物 / アルコール / アミン

Outline of Final Research Achievements

Chiral Ru-Li combined systems developed by our research group efficiently catalyzed 1) hydrocyanation of aldehydes and N-protected aldimines, 2) cyanosilylation of simple and α-alkoxy ketones, and 3) conjugate hydrocyanation of α,β-unsaturated ketones and N-acylpyrroles. The substrate-to-catalyst molar ratio of 10,000 and enantioselectivity of 99% were achieved in the best cases.
The novel chiral Ru complexes achieved 1) very rapid and highly enantioselective hydrogenation of ketones, 2) asymmetric hydrogenation of N-arylimines, quinoxalines, and benzoxazines. The rate (turnover frequency) of the hydrogenation of ketones reached about 35,000 per minute with grater than 99% enantioselectivity. The turnover number of 18,000 and enantioselectivity of 99% in the reaction of N-arylimines were obtained in the best cases.

Free Research Field

有機合成化学