Phosphorothiolates rearrangement

A mechanism, via a 6-hydroxy phosphorothiolate 8-mercapto-phosphate rearrangement, will be shown, and these new synthons will be compared with the phosphonate analogs (Wittig -Horner reagent). 

Biooxidation is an essential activation process for some organothiophosphorus neurotoxicants (1). m-Chloroperoxybenzoic acid (MCPBA) has been used to mimic some of these reactions but without identifying the products derived from phosphorothiolates (.2,3). We observed that S-alkyl phosphorothiolates react with MCPBA to form a new and unexpected class of phosphinyloxysulfonates via a novel rearrangement process (Eq. 1). 

Peracid oxidation of S alkyl phosphorothiolates (1) appears to proceed by initial formation of -oxides (2 which undergo spontaneous and very rapid rearrangement, via phosphoranoxide intermediates, to the corresponding sulfenate esters (3 that are... 

The biological properties of a phosphorothiolate S -oxide presumably depend in part on the relative rate at which it reacts as a phosphorylating agent as opposed to the rate it rearranges to the phosphinyloxysulfenate (Eq. 3). A simple experiment... 

---