A formal [3,3]-sigmatropic rearrangement route to quaternary α-vinyl amino acids: Use of allylic N-PMP trifluoroacetimidates

David B. Berkowitz, Bin Wu, Huijie Li

Research output: Contribution to journalArticle

22 Scopus citations

Abstract

Pd(II)-mediated rearrangement of allylic N-PMP (p-methoxyphenyl) trifluoroacetimidates provides the first formal sigmatropic route to quaternary, α-vinylic amino acids, potential suicide substrates for PLP enzymes. The amino acid side chains enter via transition-metal-mediated C-C bond constructions, including (i) Cu(I)-mediated conjugate addition (Ala); (ii) Pd(0)/AsPh3-mediated Stille coupling (allyl-Gly, Phe, DOPA, m-Tyr); and (iii) Pd(0)/Pt-Bu3-mediated Negishi coupling (Leu). In the synthesis of the DOPA decarboxylase inactivator, α-vinyl-m-tyrosine, the new N-PMP trifluoroacetimidate rearranges much more efficiently than the corresponding trichloroacetimidate.

Original languageEnglish (US)
Pages (from-to)971-974
Number of pages4
JournalOrganic Letters
Volume8
Issue number5
DOIs
StatePublished - Mar 2 2006

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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