A cope rearrangement in the reaction catalyzed by dimethylallyltryptophan synthase?
Louis Y P Luk1, Qi Qian, Martin E Tanner
1Department of Chemistry, University of British Columbia, Vancouver, British Columbia, Canada.
Abstract:
The enzyme dimethylallyltryptophan synthase catalyzes the "normal" prenylation of Trp at C-4 in the first step of ergot alkaloid biosynthesis. The Lys174Ala mutant is found to produce a hexahydropyrroloindole alkaloid that is "reverse-prenylated" at C-3 as its major product. This is interpreted as evidence in support of a mechanism that involves an initial "reverse-prenylation" at C-3, followed by a Cope rearrangement and rearomatization.
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