Stereoretentive synthesis and chemoselective amide-forming ligations of C-terminal peptide alpha-ketoacids.
C-Terminal peptide cyanosulfur ylides are readily converted to C-terminal peptide alpha-ketoacids, poised for chemoselective amide-forming reactions with hydroxylamines. These easily prepared and bench stable ylides are quickly and selectively oxidized with aqueous Oxone without the need for protection of most peptide side chains and with minimal epimerization. This approach offers the first method for preparing enantiomerically enriched, side chain unprotected alpha-ketoacids.
Ju
Lei
L
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
Lippert
Alexander R
AR
Bode
Jeffrey W
JW
D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry*; D007651:Keto Acids / Q000138:chemical synthesis* / Q000737:chemistry; D008024:Ligands; D008968:Molecular Conformation; D010455:Peptides / Q000737:chemistry*; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry
D000577:Amides; D007651:Keto Acids; D008024:Ligands; D010455:Peptides; D013438:Sulfhydryl Compounds