Radical hydroalkylation of olefins enabled by hydrogen atom transfer (HAT) catalysis represents a straightforward means to access C­(sp 3)-rich molecules from abundant feedstock chemicals without the need for prefunctionalization. While Giese-type hydroalkylation of activated olefins initiated by HAT of hydridic carbon–hydrogen bonds is well-precedented, hydroalkylation of unactivated olefins in a similar fashion remains elusive, primarily owing to a lack of general methods to overcome the inherent polarity-mismatch in this scenario. Here, we report the use of visible-light-driven dual HAT catalysis to achieve this goal, where catalytic amounts of an amine-borane and an in situ generated thiol were utilized as the hydrogen atom abstractor and donor, respectively. The reaction is completely atom-economical and exhibits a broad scope. Experimental and computational studies support the proposed mechanism and suggest that hydrogen-bonding between the amine-borane and substrates is beneficial to improving the reaction efficiency.

Enantioselective aryl and alkynylation of activated/nonactivated alkenes.