Absolute configuration of brevisamide and brevisin: confirmation of a universal biosynthetic process for Karenia brevis polyethers.
The discovery of brevisin, the first example of an "interrupted" polycyclic ether, obtained from the dinoflagellate Karenia brevis, posed some important questions regarding the mechanism of the cyclization process. Consequently, we have established absolute configurations of brevisin and its related metabolite brevisamide using a modified Mosher's esterification method. For brevisin, analysis was carried out on both the 31-monokis- and the 10,31-bis-MTPA esters. The results suggest that both metabolites, like other polyethers from K. brevis, result from polyepoxide precursors with uniform (S, S) configurations for all epoxides and provide further support for a universal stereochemical model for dinoflagellate polyether formation.
Center for Marine Science, University of North Carolina, Wilmington, 5600 Marvin K. Moss Lane, Wilmington, NC 28409, USA.
Ryan M
RM
Van Wagoner
Masayuki
M
Satake
Andrea J
AJ
Bourdelais
Daniel G
DG
Baden
Jeffrey L C
JL
Wright
D000470:Alkaloids / Q000737:chemistry* / Q000302:isolation & purification / Q000378:metabolism; D003500:Cyclization; D004141:Dinoflagellida / Q000737:chemistry*; D004988:Ethers, Cyclic; D005231:Fatty Acids, Unsaturated / Q000737:chemistry* / Q000302:isolation & purification / Q000378:metabolism; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D011083:Polycyclic Compounds; D011714:Pyrans; D013237:Stereoisomerism; D000095702:Polyether Toxins
D000470:Alkaloids; D004988:Ethers, Cyclic; D005231:Fatty Acids, Unsaturated; D011083:Polycyclic Compounds; D011714:Pyrans; C532303:brevisamide; D000095702:Polyether Toxins; C550958:brevisin