Visible-Light-Initiated Hydrooxygenation of Unactivated Alkenes-A Strategy for Anti-Markovnikov Hydrofunctionalization

Hydrofunctionalization of unactivated alkenes is an indispensable mean in synthetic chemistry. Given that addition of electrophilic species into alkenes intrinsically follows the Markovnikov rule, a regioselectivity switch presents a major challenge. Herein, we present a visible-light-promoted strategy for the selective anti-Markovnikov hydrooxygenation of unactivated alkenes. Therefore, an innovative reagent was carefully designed to release a highly reactive and strongly underdeveloped alkoxycarbonyloxyl radical upon reduction, which selectively adds into alkenes. Hydrogen atom abstraction from 2-phenylmalononitrile is the key to form the product. We believe that this methodology enlarges the toolbox for regioselective hydrofunctionalization and could serve as a complementary strategy to the established hydroboration/oxidation protocol.

Automated summary

This study presents a visible-light-promoted strategy for the selective anti-Markovnikov hydrooxygenation of unactivated alkenes. A carefully designed reagent releases a highly reactive and strongly underdeveloped alkoxycarbonyloxyl radical upon reduction, which selectively adds into the alkenes. This methodology expands the toolbox for regioselective hydrofunctionalization and could serve as a complementary strategy to the established hydroboration/oxidation protocol.