Synthesis of Enantioenriched Allylic Silanes via Nickel-Catalyzed Reductive Cross-Coupling

An asymmetric Ni-catalyzed
reductive cross-coupling has been developed
to prepare enantio­enriched allylic silanes. This enantio­selective
reductive alkenylation proceeds under mild conditions and exhibits
good functional group tolerance. The chiral allylic silanes prepared
here undergo a variety of stereo­specific transformations, including
intramolecular Hosomi–Sakurai reactions, to set vicinal stereogenic
centers with excellent transfer of chirality.

本研究开发出一种不对称镍催化还原交叉偶联策略，用于制备对映体富集的烯丙基硅烷。该对映选择性还原烯基化反应可在温和条件下进行，且展现出良好的官能团兼容性。本研究所制备的手性烯丙基硅烷可发生多种立体专一性转化，包括分子内Hosomi–Sakurai反应，能够构建相邻手性中心并实现优异的手性转移。