Reductive Allylic Defluorinative Cross-Coupling Enabled by Ni/Ti Cooperative Catalysis.

Unactivated alkyl chlorides are abundant building blocks in organic synthesis, but they have been rarely engaged in cross-electrophile coupling. Herein, we report a Ni/Ti-cocatalyzed reductive allylic defluorinative cross-coupling between trifluoromethyl alkenes and unactivated alkyl chlorides and bromides, enabling the efficient preparation of diverse functional-group-rich gem-difluoroalkenes. Notably, synthesis of the gem-difluoroalkene analogues of azaperone, haloperidol, and benperidol was also accomplished using our method as a key step.