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 Citations (Scopus)

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

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amino acids
routes
Amino Acids
Carboxy-Lyases
tyrosine
Suicide
Transition metals
enzymes
Metals
transition metals
Substrates
Enzymes
synthesis
3-tyrosine
trichloroacetamide

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

A formal [3,3]-sigmatropic rearrangement route to quaternary α-vinyl amino acids : Use of allylic N-PMP trifluoroacetimidates. / Berkowitz, David B; Wu, Bin; Li, Huijie.

In: Organic Letters, Vol. 8, No. 5, 02.03.2006, p. 971-974.

Research output: Contribution to journalArticle

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