Catalytic Enantioselective House–Meinwald Rearrangement: Efficient Construction of All-Carbon Quaternary Stereocenters

A catalytic asymmetric House–Meinwald rearrangement for the synthesis of both cyclic and acyclic ketones is disclosed. From readily accessible racemic tetrasubstituted epoxides, this approach provides efficient access to chiral ketones bearing α all-carbon quaternary stereocenters with high enantiocontrol. The observation of positive nonlinear effects and nontrivial kinetic feature provided important insights into the mechanism.

本研究报道了一种可用于合成环状与非环状酮的催化不对称House–Meinwald重排反应（House–Meinwald rearrangement）。该方法以易于获取的外消旋四取代环氧化物为起始原料，能够高效制备带有α位全碳季碳立体中心的手性酮，并实现了优异的对映选择性控制。对正非线性效应与非平凡动力学特征的观测，为该反应的机理研究提供了重要见解。