Enantioselective Nickel‐Catalyzed Hydrosilylation of 1,1‐Disubstituted Allenes
Tao Liu, Xin‐Rui Mao, Shuo Song, Zi‐Yang Chen, Yichen Wu, Li‐Ping Xu, Peng Wang
Abstract
Here, we report the first example of Ni-catalyzed asymmetric hydrosilylation of 1,1-disubstituted allenes with high level of regioselectivities and enantioselectivities. The key to achieve this stereoselective hydrosilylation reaction was the development of the SPSiOL-derived bisphosphite ligands (SPSiPO). This protocol features broad substrate scope, excellent functional group, and heterocycle tolerance, thus provides a versatile method for the construction of enantioenriched tertiary allylsilanes in a straightforward and atom-economic manner. DFT calculations were performed to reveal the reaction mechanism and the origins of the enantioselectivity.
Topics & Concepts
HydrosilylationEnantioselective synthesisChemistryCatalysisFunctional groupNickelStereoselectivitySubstrate (aquarium)Combinatorial chemistryStereochemistryOrganic chemistryGeologyOceanographyPolymerCatalytic C–H Functionalization MethodsOrganoboron and organosilicon chemistryAsymmetric Hydrogenation and Catalysis