Direct Synthesis of α‐Aryl‐α‐Trifluoromethyl Alcohols via Nickel Catalyzed Cross‐Electrophile Coupling

Abstract A nickel‐catalyzed reductive cross‐electrophile coupling between the redox‐active N‐ trifluoroethoxyphthalimide and iodoarenes is documented. The protocol reproduces a formal arylation of trifluoroacetaldehyde under mild conditions in high yields (up to 88 %) and with large functional group tolerance (30 examples). A combined computational and experimental investigation revealed a pivotal solvent assisted 1,2‐Hydrogen Atom Transfer (HAT) process to generate a nucleophilic α‐hydroxy‐α‐trifluoromethyl C‐centered radical for the Csp 2 −Csp 3 bond forming process.