Synthesis of Enantiomerically Pure (α‐Phenylalkyl)amines with Substituents at the ortho Position through Diastereoselective Radical Alkylation Reaction of Sulfinimines

The alkyl radical (R1) addition reaction to ortho‐X‐substituted N‐(benzylidene)‐2‐methylpropane‐2‐sulfinamides (X = Br, CN, CO2Me, OH and OMe) is highly diastereoselective, regardless of the electronic properties of the X group and the size of R1. Easy removal of the sulfinyl group provides the title compounds in enantiomerically pure form. This two‐step sequence has been successfully applied to the preparation of primary α‐(tert‐butyl)‐ortho‐hydroxy‐ and ‐ortho‐methoxybenzylamines, as well as the 3‐isopropyl‐substituted isoindolin‐1‐one.