Symmetrical and unsymmetrical 1,3-diphosphoryl substituted (E)-propenes were synthesized by the reaction of 1-acetoxyallyl substituted phosphorus compounds (phosphonates, phosphinates, and phosphine oxides) with O,O-dialkyl phosphonates (O-alkyl phosphinates, or dialkyl phosphine oxides) and bis(trimethylsilyl)acetamide (BSA) in the presence of nickel(II) chloride as catalyst, or with trivalent phosphorus acid esters (phosphites, phosphonites, and phosphinites) using only nickel(II) chloride as the catalyst.