Practical Intermolecular Hydroarylation of Diverse Alkenes via Reductive Heck Coupling

The hydroarylation of alkenes is an attractive approach to construct carbon–carbon (C–C) bonds from abundant and structurally diverse starting materials. Herein we report a palladium-catalyzed reductive Heck hydroarylation of aliphatic and heteroatom-substituted terminal alkenes and select internal alkenes with an array of (hetero)­aryl iodides. The reaction is anti-Markovnikov selective with terminal alkenes and tolerates a wide variety of functional groups on both the alkene and (hetero)­aryl coupling partners. Additionally, applications of this method to complex molecule diversifications are demonstrated. Mechanistic experiments are consistent with a mechanism in which the key alkylpalladium­(II) intermediate is intercepted with formate and undergoes a decarboxylation/C–H reductive elimination cascade to afford the saturated product and turn over the cycle.