Radical alkylation and protonation induced anti-Markovnikov hydroalkylation of unactivated olefins via cobalt catalysis.

Although strategies of olefin hydroalkylation continue to emerge rapidly, the precise control of the regio- or chemoselectivity and the expansion of the reaction range are still challenges. Herein, a straightforward route for cobalt-catalyzed anti-Markovnikov hydroalkylation of unactivated olefins with alkyl iodides has been achieved. The developed reaction is compatible with oxa-, aza-, cyclo- and a series of other functional groups as well as the frameworks of some bioactive compounds. Mechanism studies confirm that an alkyl radical is involved and cobalt-alkyl insertion followed by protonation with water are possible pathways in this reaction.