Synthesis and stereochemical confirmation of the cis-fused L/M and N/O ring systems of maitotoxin

✍ Scribed by Makoto Sasaki; Taro Nonomura; Michio Murata; Kazuo Tachibana

• Book ID: 104214529
• Publisher: Elsevier Science
• Year: 1994
• Tongue: French
• Weight: 422 KB
• Volume: 35
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)73310-7

✦ Synopsis

Stereocontr&d synthesis of &fused Iddioxadecdin system 1, which cormsponds to the L/IA and N/O rings of maimtoxin, was accomplished. Comparison of its 'H and 13C NMR data with those of the natural toxin established the earlier staeochemical assignments. Maitaoxin (m), with its molecular weight of 3422 Da, is one of the toxic principles of cigaateta food poisoningr and tire most potent toxin except for a few proteins (LDSO 50 r&kg, mouse, ip),* Recently;the full structum of MTX was elucidated to be a polyether containing 32 ether rings, and 28 hydmxyl and two sulfate groups, on the basis of extensive 2D NMR rne~u~rnen~ and CollisionaIly activated dissociation (CAD) MS/MS experiments on the whole MTX molecule and its degradation products (Figum I).2 The toxin molectie consists of both polycyclic ethers, most of which are trans-fused as is the case with brevetoxinssand ciguatoxins,4 and acyclic portions like palytoxin. 5 A remarkable structural feature is the unconventional