title: A cope rearrangement in the reaction catalyzed by dimethylallyltryptophan synthase?
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.
authors.affiliation: Department of Chemistry, University of British Columbia, Vancouver, British Columbia, Canada.
authors.forename: Louis Y P
authors.initials: LY
authors.lastname: Luk
authors.forename: Qi
authors.initials: Q
authors.lastname: Qian
authors.forename: Martin E
authors.initials: ME
authors.lastname: Tanner
mesh_terms: D019883:Alkyl and Aryl Transferases / Q000235:genetics / Q000378:metabolism*; D001232:Aspergillus fumigatus / Q000201:enzymology* / Q000235:genetics; D026121:Indole Alkaloids / Q000378:metabolism*; D016297:Mutagenesis, Site-Directed; D054876:Prenylation
chemical_list: D026121:Indole Alkaloids; D019883:Alkyl and Aryl Transferases; C032409:tryptophan dimethylallyltransferase