Ligand‐Controlled Site‐ and Enantioselective Carbene Insertion into Carbon‐Silicon Bonds of Benzosilacyclobutanes
Jingfeng Huo, Kangbao Zhong, Yazhen Xue, MyeeMay Lyu, Yifan Ping, Wenbai Ouyang, Zhenxing Liu, Yu Lan, Jianbo Wang
Abstract
Abstract We report herein a highly efficient palladium‐catalyzed carbene insertion into strained Si−C bonds of benzosilacyclobutanes, which provides an efficient method to access α‐chiral silanes. With a sterically hindered ligand, carbene insertion into the C(sp 3 )−Si bond of benzosilacyclobutanes occurred in excellent site‐ and enantioselectivity, while C(sp 2 )−Si bond insertion occurred selectively with less sterically hindered ligands. Reaction mechanism, in particular the roles of the chiral ligands in controlling the site‐selectivity of the insertion reactions, are elucidated by using hybrid density functional theory.
Topics & Concepts
CarbeneSteric effectsLigand (biochemistry)SilanesMigratory insertionInsertion reactionChemistryEnantioselective synthesisCatalysisSelectivityStereochemistryCombinatorial chemistryPhotochemistryOrganic chemistrySilaneReceptorBiochemistryCyclopropane Reaction MechanismsCatalytic Cross-Coupling ReactionsSynthetic Organic Chemistry Methods