Cross-coupling
catalysts typically react and unite functionally
distinct partners via sequential inner-sphere elementary steps: coordination,
migratory insertion, reductive elimination, etc. Here, we report a
single catalyst that cross-couples styrenes and benzyl bromides via
iterative outer-sphere steps: metal–ligand-carbon interactions.
Each partner forms a stabilized radical intermediate, yet heterocoupled
products predominate. The system is redox-neutral and, thus, avoids
exogenous oxidants, resulting in simple and scalable conditions. Numerous
variations of alkene hydrobenzylation are made possible, including
access to the privileged heterodibenzyl (1,2-diarylethane) motif and
challenging quaternary carbon variants.