Phosphorylation of 1,4:3,6-dianhydro-D-mannitol with diphenylphosphinous chloride provided a bisphosphinite derivative that, unlike what is observed in the phosphorylation with phosphorous chlorides and amides, undergoes fast phosphinite3phosphine oxide isomerization. The monophosphinite derivative, in addition, is strongly dephosphorylated. The effect of the solvents and amines (HCl acceptors) on the phosphinite3phosphine oxide isomerization is studied.