The Schmidt Reaction of Dialkyl Acylphosphonates

Milon Sprecher, Daniel Kost

Research output: Contribution to journalArticlepeer-review

47 Scopus citations

Abstract

The scope of the Schmidt rearrangement of ketones has been extended to dialkyl acylphosphonates (11a—111). Surprisingly, it was found that lla-lld and llg, in which the acyl moiety was benzoyl alone or benzoyl bearing an electron-attracting or mildly electron-releasing substituent, yielded an overwhelming portion of products resulting from C-to-N migration of the aryl group (N-arylcarbamoylphosphonates, 12, and N-arylformamides, 15). Contrariwise, the arenecarbonylphosphonates, which carry a powerful electron-releasing p-alkoxy group, yielded products resulting from phosphonate group migration from C to N or elimination (dialkyl N-arenecarbonylphosphoramidates, 13, and arenecarbonitriles, 17, respectively). These counterintuitive results are rationalized by application of the concept of“degree of electron demand”to this area of intramolecular rearrangements. The possible existence of an additional pathway for the Schmidt rearrangement, involving protonation of the iminodiazonium ion, is proposed.

Original languageEnglish
Pages (from-to)1016-1026
Number of pages11
JournalJournal of the American Chemical Society
Volume116
Issue number3
DOIs
StatePublished - 1 Feb 1994

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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