Manganese‐Mediated Homolytic Aromatic Substitution with Phosphinylidenes

Carbon-phosphorus (C−P) bond-forming reactions via homolytic aromatic substitution (HAS) of non-functionalized substrates with phosphinylidene P(O)H compounds is becoming a useful synthetic tool for the preparation of aryl and heteroaryl phosphonates, phosphinates, and phosphine oxides. This review specifically covers recent work using manganese-mediated free radical processes. Several research groups employ expensive Mn(OAc)3, whereas our own contributions focus on the novel and inexpensive Mn(OAc)2/MnO2 system.