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

Abstract

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.

Palladium-Catalyzed E-Selective Oxidative Amination of Aromatic Amine with 3-Butenoic Acid

“…Various N-nucleophiles are compatible with this reaction. 8 Pd-catalyzed oxidative amination of activated olefins with phosphorylamides to synthesize (chloro)ethenylphosphorylamides was disclosed by Xie et al 9 Jiang developed an efficient Pd-catalyzed oxidative crosscoupling of aromatic primary amines and alkenes using molecular oxygen with high levels of (Z)-enamines (Scheme 1a). 10 Although these significant efforts led to the amination of activated olefins, there has been less success in the efficient construction of C−N bonds in inactive olefins.…”