Kinetic control of proline amide rotamers: total synthesis of trans,trans- and cis,cis-ceratospongamide.
Ceratospongamide is a cyclic peptide natural product that is biosynthesized as a mixture of two proline rotamers. Remarkably, these rotamers do not detectably interconvert at temperatures up to 100 degress C. Here we report high-yielding syntheses of each rotamer and demonstrate that the threonine-derived oxazoline plays a critical role in determining the kinetic distribution of conformational isomers.
Deng
Shaojiang
S
Department of Cellular and Molecular Pharmacology, University of California, San Francisco, San Francisco, California 94143, USA.
Taunton
Jack
J
D007700:Kinetics; D010456:Peptides, Cyclic / Q000138:chemical synthesis*; D011392:Proline / Q000031:analogs & derivatives* / Q000737:chemistry; D011487:Protein Conformation; D013237:Stereoisomerism
D010456:Peptides, Cyclic; C414083:ceratospongamide; D011392:Proline