Sulfonylation in the rearrangement of an N-phosphinoyl-O-sulfonyl- hydroxylamine: demonstration of a phosphonamidic-sulfonic anhydride intermediate and ¹⁸O-labelling evidence on how it may be formed

Abstract

The rearrangement reaction of R(Ph)P(O)NHOSO₂Bn (R = PhMeCH) (57% enriched with one ¹⁸O atom in the SO₂ group) with Bu^tNH₂ in CH₂Cl₂ gives the sulfonamide BnSO₂NHBu^t (43.7% enriched with one ¹⁸O atom) as one of the products; this indicates a phosphonamidic-sulfonic anhydride intermediate [R(BnSO₂O)P(O)NHPh], formed with partial equilibration of the sulfonate oxygen atoms and attacked (in part) at the sulfonyl group.

References

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