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- The study of triester phosphorothionates was extended to peracid oxidation of individual diastereomers of cyclic phosphoramidothionate 5 under the standard reaction conditions. (Rp)-5 yields (S p)-2′ (80% diastereomeric excess) and (Sp)-5 gives (Rp)-2′ (stereochemically pure) in 45–47% yields. These stereochemical correlations show that, mechanistically, the process must differ somewhat from that for the triesters 3 4 since direct displacement of the leaving amino group by H2O as noted above would give a product with the alternative stereochemistry to that which is observed. This implies that the endocyclic amino leaving group is not in an apical position in the initially-formed trigonal bipyramid, perhaps because of steric constraints associated with the fivemembered ring and/or the poor apicophilicity of the nitrogen atom. Therefore, the nitrogen leaving group may be displaced from an equatorial position or the initial trigonal bipyramid may undergo pseudorotation in which the leaving group then takes an apical position. In either case cleavage of the P-N bond yields similar intermediates to those described above leading to the final hydrogenphosphonate