Phosphonation of arenes with dialkyl phosphites catalyzed by Mn(II)/CO(II)/O2 redox couple

Arylphosphonates were first synthesized through a catalytic phosphonation of various arenes with dialkyl phosphites under the influence of an Mn(OAc)(2)/Co(OA(C))(2)/O-2 redox couple. For instance, the reaction of benzene with diethyl phosphite in the presence of Mn(OAc)(2) (5 mol %) and Co(OAc)(2) (1 mol %) under a mixed gas of O-2 (0.5 atm) and N-2 (0.5 atm) at 45 degrees C led to diethyl phenylphosphonate in 81% selectivity at 62% conversion. This is the first successful phosphonation of benzene with dialkyl phosphites through a catalytic radical process.