有机化学 ›› 2017, Vol. 37 ›› Issue (1): 47-78.DOI: 10.6023/cjoc201606024 上一篇    下一篇

综述与进展

手性Binap-Ru(II)催化剂用于不对称加氢反应的研究进展

高安丽, 叶青松, 余娟, 刘伟平   

  1. 昆明贵金属研究所 稀贵金属综合利用新技术国家重点实验室 昆明 650106
  • 收稿日期:2016-06-14 修回日期:2016-08-12 出版日期:2017-01-25 发布日期:2016-09-01
  • 通讯作者: 刘伟平 E-mail:liuweiping0917@126.com
  • 基金资助:

    国家“十二五”科技支撑计划课题(No. 2012BAE06B08)和云南省科技创新强者计划(Nos. 2015AA006,2013B019)资助项目.

Research Advances of the Chiral Binap-Ru(II) Catalysts in Asymmetric Hydrogenation Reactions

Gao Anli, Ye Qingsong, Yu Juan, Liu Weiping   

  1. State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals, Kunming Institute of Precious Metals, Kunming 650106
  • Received:2016-06-14 Revised:2016-08-12 Online:2017-01-25 Published:2016-09-01
  • Supported by:

    Project supported by the 12th National Scientific Support Plan(No. 2012BAE06B08) and the Yunnan Province Scientific Creative Plan(Nos. 2015AA006, 2013B019).

手性联二萘基双膦配体Binap由一对2-二苯基膦萘基连接1和1'位组成,具C2-对称框架轴向手性,比旋光度达到±234°.Binap配体可以和许多过渡金属形成稳定的螯合状配合物,在催化过程中通过金属中心“传递”立体空间效应,诱导不对称催化反应.针对Binap-Ru(Ⅱ)催化体系,以体系中形成的稳定配合物为主线,详细介绍反应过程中涉及到的底物分子种类、反应条件、产物的对映选择性等以及可能的反应机理,以期对该体系有深入的理解.特别关注该体系的不对称催化应用合成.

关键词: Binap配体, 手性钌配合物, 不对称催化, 反应机理, 应用

Chiral 2,2'-bis(diphenylphosphino)-1,1'-binapthyl(Binap) ligand consists of a pair of 2-diphenylphosphinonaphthyl groups connected at the 1 and 1'positions,being of the nature of the C2-axial chirality with optical activity of ±234°.The Binap can coordinate with many transitional metals to form stable chelation complexes,effecting the chirality transfer to the metal center for function in asymmetrically catalytic reactions.This contribution is focused on the Binap-Ru(Ⅱ) catalytic system that covers the various substrates,reaction conditions,enantioselectivity of the products,reaction mechanism,and others on the basis of the prepared stable Binap-Ru(Ⅱ) complexes as the clue in the text.This study will give a deep understanding of this system especially concerning the applied catalytic synthesis of the useful organic molecules.

Key words: Binap ligand, chiral ruthenium complexes, asymmetric catalysis, reaction mechanism, application