Rhodium(I)-Catalyzed Highly Enantioselective Insertion of Carbenoid into Si–H: Efficient Access to Functional Chiral Silanes Diao Chen Dong-Xing Zhu Ming-Hua Xu 10.1021/jacs.5b12960.s002 https://acs.figshare.com/articles/dataset/Rhodium_I_Catalyzed_Highly_Enantioselective_Insertion_of_Carbenoid_into_Si_H_Efficient_Access_to_Functional_Chiral_Silanes/2072710 The first rhodium­(I)-catalyzed enantioselective Si–H insertion reaction of α-diazoesters and α-diazophosphonates has been developed. The use of a <i>C</i><sub>1</sub>-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. 2016-02-04 19:24:59 α- diazoesters C 1 insertion stereochemical pathway DFT calculations chiral diene ligand chiral α- silyl esters isotope effect experiments Functional Chiral Silanes α- diazophosphonates Enantioselective Insertion