Electrocatalyzed addition of dialkyl phosphonates to aromatic carbonyl compounds. A convenient preparation of phosphoric esters via an efficient rearrangement

Abstract

Upon brief cathodic electrolysis in DMF solutions containing a tetraalkylammonium salt, the addition reaction of dialkyl phosphonates to various aromatic aldehydes ketones resulted in an unusual formation of mixed trialkyl phosphates via PO rearrangement. The formation of α-hydroxyalkanephosphonates as the well-known carbonyl adduct was observed for the case of aliphatic carbonyl compounds. The reaction-path is described in terms of the electrocatalytic generation of dialkyl phosphonate anions and an efficient PO rearrangement in the intermediate adduct anions.