Lossen-like rearrangement of N-[α-methylbenzyl(phenyl)phosphinoyl]-O-methylsulfonylhydroxylamine with methylamine: retention of configuration at phosphorus as revealed by X-ray crystallography

The Lossen rearrangement involves thermal or alkaline conversion of hydroxamic acid into an isocyanate via the intermediacy of its O ‐acyl, sulfonyl, or phosphoryl derivative. In the presence of water, amine, or alcohol, the isocyanate is converted into amine, urea or urethane, respectively. This reaction occurs via a similar mechanism of Curtius rearrangement or Hofmann rearrangement by means of the formation of a univalent nitrogen intermediate (known as nitrene). The study finds that the rearrangement rate is directly proportional to the acidity of the leaving group or the conjugate acid of the leaving group. This rearrangement has been modified to occur under different conditions and has been applied in the preparation of amine, urea, and urethane derivatives.

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Rearrangements of Hydroxylamines, Oximes and Hydroxamic Acids

Pereira

Santos²

2010

Patai's Chemistry of Functional Groups

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Introduction The [3,3]‐Sigmatropic Rearrangements The [2,3]‐Sigmatropic Rearrangements The Dyotropic Rearrangements The B amberger Rearrangements The B eckmann Rearrangements The N eber Rearrangements The L ossen Rearrangement Other Rearrangements

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Lossen-like rearrangement of N-[α-methylbenzyl(phenyl)phosphinoyl]-O-methylsulfonylhydroxylamine with methylamine: retention of configuration at phosphorus as revealed by X-ray crystallography

Abstract: The diastereoisomers of the title compound 6 rearrange with high stereospecificity on treatment with MeNH2, giving PhMeCHP(O)(NHMe)NHPh in which the migrating phenyl group has been replaced by MeNH2 with retention of configuration a t phosphorus.

Cited by 5 publications

References 8 publications

N,O-Bis(trimethylsilyl)hydroxylamine

N,O-Bis(trimethylsilyl)hydroxylamine

Lossen Rearrangement

Rearrangements of Hydroxylamines, Oximes and Hydroxamic Acids

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