Structure and Absolute Stereochemistry of Fusaproliferin, a Toxic Metabolite from Fusarium proliferatum

Abstract

Fusaproliferin is a toxic sesterterpene isolated from Fusarium proliferatum, a widespread pathogen of cereals. Its absolute configuration has been determined by single crystal X-ray diffraction analysis. Fusaproliferin is considered to be a sesterterpene with a new ring skeleton having four C = C double bonds and four chiral atoms. The configurations of the four chiral atoms C10, C14, C15, and C19 are (R), (S), (R), and (S), respectively. In the solid state the macrolide shows a concave hydrophobic surface and hydrophilic convex face. The absolute configuration of C14 and C15 is the same as that observed for retigeranic acid, consistent with fusaproliferin being formed via a sesterterpenic-type biosynthetic pathway.

The occurrence of "emerging" mycotoxins in brewing raw materials.

“…Moniliformin má strukturu hydroxycyklobutenedionu, tedy malé iontové molekuly ve formě sodné nebo draselné soli karboxylové kyseliny (Springer et al, 1974). Fusaproliferin je bicyklický seskviterpen (Santini at al., 1996). Podrobný přehled o fyzikálně chemických a biologických vlastnostech těchto mykotoxinů a jejich významu v potravinovém řetězci shrnuje práce Jestoi v roce 2008 (Jestoi, 2008).…”

“…Moniliformin hydroxycyclobutanedione structure is formed by small ionic molecules in a form of natrium or potassium acid (Springer et al, 1974). Fusaproliferin is a bicyclic sesquiterpene (Santini et al, 1996). A detailed summary of physical, chemical and biological characters of these mycotoxins and their importance in the food chain has been presented in a study by Jestoi (Jestoi, 2008).…”

Structure elucidation of 11-epiterpestacin glycoside (11-ETG) isolated from Bipolaris sorokiniana NSDR-011

“…In the course of our search for new phytotoxic substances from plant pathogenic fungi, we previously reported that a pair of bicyclo 5-15-fused sesterterpene isomers, referred to as terpestacin (Oka et al 1993) and 11-epiterpestacin (11-ET, 2), were isolated from the cultures of two distinct fungal strains, B. sorokiniana and B. cynodontis, respectively (Lim et al 1995;Lim et al 1996;Nihashi et al 2002). From the culture of B. sorokiniana, an acetylated derivative of 11-ET, fusaproliferin (3) was also isolated (Santini et al 1996). In this paper, we report the isolation and structural analysis of another terpestacin-related compound, 11-ETG (1), which was found in the culture of B. sorokiniana.…”

Phytotoxic Sesterterpene, 11-Epiterpestacin, fromBipolaris sorokinianaNSDR-011

“…Its stereostructure has been established by NMR, molecular dynamics calculation, and single crystal X-ray diŠrac-tion analyses. 7,8) The results of these studies indicate that the diŠerences between terpestacin and fusaproliferin are determined by whether the primary hydroxy group at C-24 is acetylated or not, and by the absolute conˆguration at C-11, one of four asymmetric centers, in these compounds. The absolute conˆguration at C-11 of terpestacin is S, while that at the corresponding carbon of fusaproliferin (referred to as C-10 in this compound) is R. It has also been brie‰y mentioned that 24-deacetylfusaproliferin, whose planar structure is the same as that of terpestacin, was present in the cultureˆltrate of F. proliferatum.…”