Structures of two stereoisomers of a new type of indoloditerpene related to the tremorgenic mycotoxin paxilline, from Emericell desertorum and Emericella striata

Journal of the Chemical Society, Chemical Communications
1987.0

Abstract

The structure elucidation of emindoles DA (1) and SA (2), indoloditerpenes from the mycelial extracts of Emericella desortorum and Emericella striata, respectively, is reported based on their 1H and 13C n.m.r. spectra and an X-ray crystallographic study of emindole DA monoacetate (4); these are novel proto-type indoloditerpenes biologically related to the tremorgenic mycotoxin paxilline (3). Emindole DA (1) and emindole SA (2) were isolated from the mycelial hexane extract of E. desertorum and the mycelial acetone extract of E. striata, respectively. Their empirical formula C28H39NO was confirmed by electron-impact mass spectrometry and elemental analysis. The structure of emindole DA (1) was determined by n.m.r. data and X-ray crystallography of its monoacetate (4), while emindole SA (2) showed similar spectral data indicating it is a stereoisomer of (1). The isolation of these stereoisomers along with paxilline (3) suggests two biosynthetic pathways for diterpene moiety cyclization in the fungi: one leading to paxilline via carbon skeleton migration after cyclization, and the other producing emindoles DA and SA via partial cyclization.

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