• 文献标题:   Stepwise Construction of Ru(II)Center Containing Chiral Thiourea Ligand on Graphene Oxide: First Efficient, Reusable, and Stable Catalyst for Asymmetric Transfer Hydrogenation of Ketones
  • 文献类型:   Article
  • 作  者:   MAYAKRISHNAN G, SOO KI, MIN CI
  • 作者关键词:   graphene, chiral thiourea ligand, heterogenization, asymmetric reaction, reuse, recovery
  • 出版物名称:   CATALYSTS
  • ISSN:  
  • 通讯作者地址:   Konkuk Univ
  • 被引频次:   0
  • DOI:   10.3390/catal10020175
  • 出版年:   2020

▎ 摘  要

Heterogenization of homogenous catalysts on solid support has attracted tremendous attention in organic synthesis due to the key benefits of heterogenized catalysts such as easy recovery and reusability. Although a considerable number of heterogenized catalysts are available, to the best of our knowledge, there is no efficient and reusable heterogenized catalyst reported for asymmetric reactions to date. Herein, we prepared a [RuCl2(eta(6)-p-cymene)]/chiralthiourea ligand covalently bonded to graphene nanosheets (G-CLRu(II), where G represents graphene oxide (GO), CL denotes chiral N-((1-phenylethyl)carbamothioyl)acetamide and Ru(II) symbolizes [RuCl2(eta(6)-p-cymene)]), for the asymmetric transfer hydrogenation of ketones. Five simple steps were involved in the preparation of the G-CLRu(II) catalyst. The structure of G-CLRu(II) was investigated by means of various spectroscopic and microscopic techniques. Coordination mode and covalent bonding involved in the G-CLRu(II) structure we reconfirmed. G-CLRu(II) demonstrated good catalytic performance towards the asymmetric transfer hydrogenation of ketones (conversion of up to 95%, enantiomeric excesses (ee) of up to 99%, and turnover number (TON) and turnover frequency (TOF) values of 535.9 and 22.3 h(-1), respectively). A possible mechanism is proposed for the G-CLRu(II)-catalyzed asymmetric transfer hydrogenation of ketones. Recovery (similar to 95%), reusability (fifth cycle, yield of 89% and ee of 81%), and stability of G-CLRu(II) were found to be good. We believe that the present stepwise preparation of G-CLRu(II) opens a new door for designing various metal-centered heterogenized chiral catalysts for asymmetric synthesis.