Citation

Berkowitz DB, Wu B, Li H. Org. Lett. 2006; 8(5): 971-974.

Copyright

(Copyright © 2006, American Chemical Society)

DOI

10.1021/ol060019s

PMID

16494487

PMCID

PMC2504469

Abstract

Pd(II)-mediated rearrangement of allylic N-PMP (p-methoxyphenyl) trifluoroacetimidates provides the first formal sigmatropic route to quaternary, alpha-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, alpha-vinyl-m-tyrosine, the new N-PMP trifluoroacetimidate rearranges much more efficiently than the corresponding trichloroacetimidate.

Language: en

Keywords

Amino Acids; Catalysis; Hydrocarbons, Fluorinated; Imidoesters; Molecular Structure; Palladium; Stereoisomerism