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