Ligand-Controlled Site- and Enantioselective Carbene Insertion into Carbon-Silicon Bonds of Benzosilacyclobutanes.
Jingfeng HuoKangbao ZhongYazhen XueMyeeMay LyuYifan PingWenbai OuyangZhenxing LiuYu LanJianbo WangPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2022)
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.