Difluorocarbene-Enabled Selective Cleavage and Reconstruction of Aliphatic Tertiary Amine C sp ³ –N Bonds

In this study, a metal-free and efficient method for the synthesis of primary, secondary, tertiary amines via difluorocarbene-enabled selective aliphatic tertiary amine Csp3–N bond cleavage/Csp3–N bond formation has been developed. In those reactions, in situ generated difluoromethylammonium ylides were the key intermediates for the direct deaminative amination. This method featured mild reaction conditions, good functional group tolerance, and ease of execution with 104 examples, and it was suitable for late-stage modification of pharmaceuticals.