The Complete Structure of Maitotoxin, Part II: Configuration of the C135C142 Side Chain and Absolute Configuration of the Entire Molecule

Inhibition of Maitotoxin‐Induced Ca2+ Influx in Rat Glioma C6 Cells by Brevetoxins and Synthetic Fragments of Maitotoxin

“…Electrophysiological studies have disclosed several characteristics of this nonselective channel, including ion selectivity and the current-voltage relationship (Kobayashi et al, 1987;Faivre et al, 1990;Dietl and Völkl, 1994;Worley et al, 1994;Estacion et al, 1996;Nishio et al, 1996), but its molecular makeup remains unknown. The complete structure of MTX (Scheme 1, structure 1) has recently been shown to consist of a ladder-shaped polyether skeleton (Murata et al, 1994;Nonomura et al, 1996;, as is often seen for other dinofiagellate metabolites such as ciguatoxins and brevetoxins. These studies have also demonstrated that MTX is an amphiphilic compound; it consists of a hydrophilic polyhydroxyl portion from Cl to ring Q and a hydrophobic fused-polycyclic portion fromring R to ring F'.…”

Biomimetic Synthesis of Polyether Natural Products via Polyepoxide Opening

“…This creates a repeating C-C-O sequence that stretches throughout the polycyclic core of these molecules (Figure 15.6). The first isolated member of this family, brevetoxin B (44), was reported by Nakanishi and Clardy in 1981 [81] and was followed by numerous others, including maitotoxin [82][83][84], the largest nonpolymeric molecule isolated from natural sources to date. The minimal availability combined with the unprecedented size of ladder polyethers have inspired herculean endeavors in the isolation and structural characterization of these compounds and have pushed the limits of analytical methods, including chromatography, mass spectrometry, NMR, and X-ray diffraction [85].…”

Die Entdeckung und Synthese von marinen Polyethern

“…[ [125] Kürzlich äußerten Gallimore und Spencer Zweifel an der korrekten Zuordnung der stereochemischen Verhältnisse für C51 und C52 (Verknüpfung der Ringe J und K). [34] Ihre Kritik fußte auf Nakanishis Hypothese [33] zur Biosynthese der Leiterstruktur von marinen Polyethern und schien zunächst logisch zu sein.…”