Palladium/Copper‐Mediated Switchable Approaches towards (Chloro)ethenylphosphorylamides by Phosphorylamides and Alkenes

A switchable access to ethenylphosphorylamides and chloroethenylphosphorylamides from phosphorylamides and alkenes has been disclosed herein. With the assistance of Pd(OAc)2, a catalytic loading of CuCl2 or CuBr (20 mol‐%) led to the occurrence of dehydrogenative cross coupling reactions with high efficiency and broad substrate scope, while 1.0 equivalent of CuCl2 rendered the dehydrogenative amidochlorination reactions to take place with high stereoselectivity. A switchable formation of chloro‐ and enephosphorylamides from phosphorylamides and alkenes was disclosed herein. In the presence of Pd(OAc)2, a catalytic loading of CuBr or CuCl2 (20 mol‐%) led to the occurrence of dehydrogenative cross coupling reactions, while 1.0 equivalent of CuCl2 rendered the dehydrogenative amidochlorination reactions to take place in a stereoselective manner.