An Olefinic 1,<scp>2‐<i>α</i>‐Boryl</scp> Migration Enables 1,<scp>2‐Bis</scp>(boronic esters) via <scp>Radical‐Polar</scp> Crossover Reaction

Comprehensive Summary A radical‐induced 1,2‐ α ‐boryl migration through radical polar crossover reactions has been described. In this work, in situ formed vinyldiboron “ate” complexes from alkenyl Grignard reagent and diborylalkanes react with commercial radical precursors under light initiation. This three‐component process enables diborylation of alkene. This protocol features high atom economy, a broad substrate scope as well as good functional group toleration with mild conditions.