ja5b12960_si_001.pdf (6.87 MB)
Rhodium(I)-Catalyzed Highly Enantioselective Insertion of Carbenoid into Si–H: Efficient Access to Functional Chiral Silanes
journal contribution
posted on 2016-02-04, 19:24 authored by Diao Chen, Dong-Xing Zhu, Ming-Hua XuThe 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.