Hirao Reaction Research Articles

Development of a room temperature Hirao reaction

Arylphosphonates were prepared at 25 °C through the palladium-catalyzed coupling of aryl iodides with a silver phosphonate. A wide range of aryl iodides were successfully employed including phenolic substrates as well as those containing an ortho substituent.

Revisiting the Hirao cross-coupling: improved synthesis of aryl and heteroaryl phosphonates

The palladium-catalyzed cross-coupling of dialkylphosphite with aromatic electrophiles (Hirao coupling) was re-investigated. Some limitations in terms of palladium loadings and substrate reactivity are alleviated with the use of Pd(OAc) 2 complexed to 1,1′-bis(diphenylphosphino)ferrocene (dppf) as a ligand. Various aryl and heteroaryl halides are employed to deliver both known and novel substituted phosphonates. The first examples of aryl chloride couplings are also reported.