Revision of the structure of isochaetoglobosin Db based on NMR analysis and biosynthetic consideration

Abstract

Isochaetoglobosin D_b is a new chaetoglobosin possessing a unique 3,4-substituted pyrrole ring isolated and named by Qiu et al., and it is different from any one of the 14 sub-types in the macrocyclic ring of chaetoglobosins classified in our previous work. Its chemical shift values, coupling constants and biosynthetic consideration implied that the proposed structure of isochaetoglobosin D_b was incorrect. In this report, based on detailed NMR data analysis together with biosynthetic consideration, the structure of isochaetoglobosin D_b is suggested to be revised to that of penochalasin C. The NMR spectra of penochalasin C measured in the same solvent (DMSO-d₆) as that of isochaetoglobosin D_b supported the above conclusion. The results imply that reasonable biosynthetic consideration could complement spectroscopic structural determination, and also support that the ¹H-NMR rule of chaetoglobosin summarized in our previous work can provide help for dereplication and rectification.