Base induced rearrangement reactions of N-phosphinoyl-O-sulfonylhydroxylamines. Observation of a phosphanamidic-sulfonic anhydride intermediate by NMR spectroscopy

Authors
Harger, MJP Sreedharan-Menon, R
Citation
Mjp. Harger et R. Sreedharan-menon, Base induced rearrangement reactions of N-phosphinoyl-O-sulfonylhydroxylamines. Observation of a phosphanamidic-sulfonic anhydride intermediate by NMR spectroscopy, J CHEM S P2, (2), 1999, pp. 159-163
Citations number
20
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
ISSN journal
03009580 → ACNP
Issue
2
Year of publication
1999
Pages
159 - 163
Database
ISI
SICI code
0300-9580(199902):2<159:BIRRON>2.0.ZU;2-7
Abstract
The hydroxylamine derivative PhRP(O)NHOSO2Me (R = PhMeCH) reacts with (BuNH 2)-N-t to give the rearrangement product RP(O)(NHPh)NHBut by way of a react ive but non-transient intermediate. At low amine concentrations the interme diate can be observed by P-31 NMR spectroscopy; it is thought to be the mix ed anhydride RP(O)(NHPh)OSO2Me as it has the same chemical shift as an auth entic sample generated from RP(O)(NHPh)Cl and AgOSO2Me. The intermediate is formed with high (or complete) stereospecificity but it reacts with (BuNH2 )-N-t with low stereospecificity.