Total Synthesis and Reassignment of the Structures of the Antimicrobial Lipodepsipeptides Circulocin γ and δ

Autor:	Katrina A. Jolliffe, James R. Cochrane, Claudia J. Exner
Rok vydání:	2015
Předmět:	chemistry.chemical_classification Molecular Structure Chemistry Stereochemistry Organic Chemistry Absolute configuration Fatty acid Total synthesis Coupling reaction chemistry.chemical_compound Anti-Infective Agents Depsipeptides Side chain Molecule Epimer Methylene Antimicrobial Cationic Peptides
Zdroj:	The Journal of Organic Chemistry. 80:4491-4500
ISSN:	1520-6904 0022-3263
DOI:	10.1021/acs.joc.5b00349
Popis:	The structures of the naturally occurring antimicrobial lipodepsipeptides circulocin γ and circulocin δ have been reported to comprise a common cyclic depsipeptide core attached to 3-hydroxy,ω-guanidino fatty acid chains differing in length by two methylene units, but analysis of the reported data suggested that the originally reported structures had incorrect side chain lengths. The total synthesis of both side chain epimers of the originally reported structure of circulocin γ bearing a 19-guanidino-3-hydroxynonadecanoyl (GHND) side chain has been accomplished using a modular approach involving synthesis of the cyclic depsipeptide and side chain fragments followed by a late stage coupling reaction. This revealed that the originally reported structure for circulocin γ bearing the GHND side chain is incorrect and that this structure is actually that of circulocin δ. It has also enabled the absolute configuration of the side chain hydroxy group of the natural product to be assigned as (R). Subsequent synthesis of the analogue bearing a 17-guanidino-3-(R)-hydroxyheptadecanoyl (GHHD) side chain provided confirmation that this revised structure is that of circulocin γ.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::27390fd14a5ff1ac32a18e2b34f4f7ba https://doi.org/10.1021/acs.joc.5b00349 Zobrazit plný text záznamu