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Regiodivergent N[BOND]C and N[BOND]N Aryl Coupling Reactions of Indoloterpenes and Cycloether Formation Mediated by a Single Bacterial Flavoenzyme

Authors


  • M.B. and L.D. contributed equally to this work. Financial support by the BMBF (GenBioCom) is gratefully acknowledged. We thank Wiebke Karguth for assistance in molecular studies, A. Perner and H. Heineke for MS and NMR measurements, and M. Roth and M. Steinacker for support with fermentations.

Abstract

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Radical diversification: Through the discovery of diverse indolosesquiterpene dimers in a strain heterologously expressing the xiamycin biosynthesis genes, the analysis of mutants, and biotransformation studies, it has been inferred that a single flavoprotein mediates N[BOND]C and N[BOND]N aryl coupling reactions, as well as the formation of a cyclic ether (oxiamycin). Synthetic emulation of this unusual transformation provides evidence for a radical-based mechanism.

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