Low-Valent Tungsten Catalysis Enables Site-Selective Isomerization–Hydroboration of Unactivated Alkenes

A tungsten-catalyzed hydroboration of unactivated alkenes at distal C­(sp3)–H bonds aided by native directing groups is described herein. The method is characterized by its simplicity, exquisite regio- and chemoselectivity, and wide substrate scope, offering a complementary site-selectivity pattern to other metal-catalyzed borylation reactions and chain-walking protocols.