Asymmetric total synthesis and stereochemical revision of gymnangiamide.
The asymmetric total synthesis of the originally proposed structure of gymnangiamide, a cytotoxic pentapeptide isolated from the marine hydroid Gymnangium regae Jaderholm, has been achieved. Key to the synthesis was the use of asymmetric hydrogenation of alpha-substituted beta-ketoesters through dynamic kinetic resolution for the preparation of nonproteinogenic chiral amino acids. The disparity of the NMR spectra between the synthetic material containing the L-serine residue and the natural product required a revision of the proposed structure.
Laboratoire Charles Friedel, ENSCP Chimie ParisTech, UMR 7223, 11 rue P. et M. Curie, F-75231 Paris Cedex 05, France.
Hitoshi
H
Tone
Marie
M
Buchotte
Céline
C
Mordant
Eric
E
Guittet
Tahar
T
Ayad
Virginie
V
Ratovelomanana-Vidal
D000818:Animals; D006829:Hydra / Q000737:chemistry; D008386:Marine Biology; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D009842:Oligopeptides / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D013237:Stereoisomerism
D009842:Oligopeptides; C487670:gymnangiamid