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Rhodium(I)-Catalyzed Highly Enantioselective Insertion of Carbenoid into Si–H: Efficient Access to Functional Chiral Silanes

Author:
Chen, Diao, Zhu, Dong-Xing, Xu, Ming-Hua
Source:
Journal of the American Chemical Society 2016 v.138 no.5 pp. 1498-1501
ISSN:
1520-5126
Subject:
deuterium, enantiomers, esters, isotopes, ligands, phosphonates, rhodium, 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.
Agid:
5487605