Iron‐Catalyzed Markovnikov Hydration of Unactivated Terminal Alkenes Enabled by Reductive Radical‐Polar Crossover

Herein, we describe a simple and convenient protocol for the Markovnikov oxidation of unactivated olefins to alcohols and ketones using readily available iron salt Fe(acac)3 as a catalyst, and phenylsilane PhSiH3 as reducing material. All reactions proceed efficiently at mild conditions with air as terminal oxidant. This transformation has been applied to a variety of substrates, and is distinguished by its simplicity, mild temperatures and broad scope. The alcohols are formed smoothly in up to >80% isolated yield and with 100% regioselectivity for secondary alcohols formation, while the corresponding ketones were observed as by‐products.