Aliphatic Radical Relay Heck Reaction at Unactivated C(sp3)–H Sites of Alcohols

The Mizoroki−Heck reaction is one of the most efficient methods for alkenylation of aryl, vinyl, and alkyl halides. Due to its innate nature, this protocol requires the employment of compounds possessing a halogen atom at the site of functionalization. However, the accessibility of organic molecules possessing a halogen atom at a particular site in aliphatic systems is extremely limited. Thus, a protocol that would allow a Heck reaction to occur at a specific non-functionalized C(sp3)−H site would be highly desirable. Here, we report a radical relay Heck reaction which allows for a selective remote alkenylation of aliphatic alcohols at unactivated β-, γ- and δ-C(sp3 20 )–H sites. The use of easily installable/removable Si-based auxiliary enables selective I-atom/radical translocation events at remote C−H sites followed by the Heck reaction. Notably, the reaction proceeds smoothly under mild visible light-mediated conditions at room temperature, producing highly modifiable and valuable alkenol products from readily available alcohols feedstocks.