Pd-Catalyzed Hirao P–C Coupling Reactions with Dihalogenobenzenes without the Usual P-Ligands under MW Conditions

A literature survey of the P–C coupling reactions 1,4-and 1,2-bromo-iodobenzenes with diphenylphosphine oxide or diethyl phosphite under different conditions comprising Pd-, Ni-, Cu-catalysis revealed that, depending on experimental details, yields corresponding >P(O)-bromobenzenes were rather diverse and occasionally contradicting. Therefore, reactivity a series 1,4-, 1,3- 1,2-dibromo- bromo-iodobenzenes above mentioned P-reagents was evaluated “P-ligand-free” microwave (MW)-assisted elaborated by us. Starting from dibromobenzenes iodo-bromoarenes, practical competent syntheses developed for phosphonoyl- phosphinoyl-bromoarenes, and, in few instances, arenes two P-functions. The cheaper may be substituted bromo-iodo derivatives. In all, 12 products prepared 45–82%. They fully characterized. method described does not require use traditional P-ligands.