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 sp³ α-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 β-peroxy alcohols and β-hydroxyketones correspondingly with excellent functional group tolerance. The resulting β-peroxy alcohols could be further transformed into β-hydroxyynones and propargylic 1,3-diols.