Asymmetric syntheses of APTO and AETD: the β-amino acid fragments within microsclerodermins C, D, and E

J Org Chem. 2013 Mar 15;78(6):2500-10. doi: 10.1021/jo302731m. Epub 2013 Feb 21.

Abstract

Efficient asymmetric syntheses of APTO and AETD, the highly functionalized β-amino acid fragments within microsclerodermins C, D, and E, are reported. The conjugate addition of lithium (R)-N-benzyl-N-(α-methylbenzyl)amide to tert-butyl (E,E)-7-(triisopropylsilyloxy)hepta-2,4-dienoate and in situ enolate oxidation with (-)-camphorsulfonyloxaziridine, diastereoselective dihydroxylation of a 2,3-syn-γ,δ-unsaturated-α-hydroxy-β-amino ester derivative under Donohoe conditions, and a Julia-Kocieński olefination were used as the key steps.

MeSH terms

  • Amino Acids, Neutral / chemical synthesis*
  • Amino Acids, Neutral / chemistry*
  • Lithium / chemistry*
  • Molecular Structure
  • Oxidation-Reduction
  • Peptide Fragments / chemical synthesis*
  • Peptide Fragments / chemistry*
  • Peptides, Cyclic / chemical synthesis*
  • Peptides, Cyclic / chemistry
  • Stereoisomerism

Substances

  • Amino Acids, Neutral
  • Peptide Fragments
  • Peptides, Cyclic
  • microsclerodermin C
  • microsclerodermin D
  • microsclerodermin E
  • Lithium