LiBr‐Mediated Cross‐Coupling towards α‐Trifluoromethylamines

Abstract A LiBr‐mediated cross‐coupling reaction between organozinc reagents and α‐chloro trifluoromethyl amines for modular access to α‐trifluoromethyl amines is reported. Different kinds of alkyl‐ and arylzinc reagents are compatible with this LiBr‐mediated cross‐coupling, resulting in a number of diversified α‐trifluoromethyl amines in high yields. This method features easy operation, mild reaction conditions, excellent functional group tolerance, and broad substrate scope. Preliminary mechanistic insight suggests that this cross‐coupling reaction involves α‐trifluoromethyl imine formation from α‐chloro trifluoromethyl amines under LiX (X=Cl, Br). The synthetic utility of this method is successfully demonstrated by a gram‐scale reaction and diverse product transformations.