Rhodium(I)-Catalyzed Highly Enantioselective Insertion of Carbenoid into Si–H: Efficient Access to Functional Chiral Silanes
2016-02-04T19:24:59Z (GMT) by
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.
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