Mimicking Dimethylallyltryptophan Synthase: Experimental Evidence for a Biosynthetic Cope Rearrangement Process

Abstract

Easy to cope with: Experimental evidence was found to support an enzymatic [3,3]-sigmatropic rearrangement catalyzed by dimethylallyltryptophan (DMAT) synthase (see scheme). A bio-inspired system showed the feasibility of Cope rearrangement to the C-4 position of the indole nucleus. The tricyclic benzo[cd]indole core of welwitindolinones and dragmacidin E was synthesized using this transformation.