title: Rhodium(I)-Catalyzed Highly Enantioselective Insertion of Carbenoid into Si-H: Efficient Access to Functional Chiral Silanes.
abstract: The first rhodium(I)-catalyzed enantioselective Si-H insertion reaction of α-diazoesters and α-diazophosphonates has been developed. The use of a C1-symmetric chiral diene ligand enabled the asymmetric reaction to proceed under exceptionally mild conditions and give versatile chiral α-silyl esters and phosphonates with excellent enantioselectivities (up to 99% ee). The mechanism and stereochemical pathway of this novel Rh(I)-carbene-directed Si-H insertion was investigated by deuterium kinetic isotope effect experiments and DFT calculations.
authors.affiliation: State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences , 555 Zuchongzhi Road, Shanghai 201203, China.
authors.forename: Diao
authors.initials: D
authors.lastname: Chen
authors.affiliation: State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences , 555 Zuchongzhi Road, Shanghai 201203, China.
authors.forename: Dong-Xing
authors.initials: DX
authors.lastname: Zhu
authors.affiliation: State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences , 555 Zuchongzhi Road, Shanghai 201203, China.
authors.forename: Ming-Hua
authors.initials: MH
authors.lastname: Xu