Copper- and Cobalt-Catalyzed Direct Coupling of sp3 α-Carbon of Alcohols with Alkenes and Hydroperoxides

A zerovalent copper- and cobalt-catalyzed direct coupling of the sp(3) alpha-carbon of alcohols with alkenes and hydroperoxides was developed in which the hydroperoxides acted as radical initiator and then coupling partner. 1,3-Enynes and vinylarenes underwent alkylation-peroxidation to give beta-peroxy alcohols and beta-hydroxyketones correspondingly with excellent functional group tolerance. The resulting beta-peroxy alcohols could be further transformed into beta-hydroxyynones and propargylic 1,3-diols.