Catalytic hydrophosphorylation of dialkyl 2-allylmalonates

The reaction of dialkyl hydrogen phosphites and diphenylphosphine oxide with dialkyl 2-allylmalonates in the presence of [Pd(Ph3P)(4)] is studied. The addition of the hydrophosphoryl compounds to the multiple bond is established to proceed by the Markovnikov rule. The reaction is accompanied by the side process of malonate dealkoxycarbonylation whose contribution to the main process depends on the nature of the reagents.