A Cope Rearrangement in the Reaction Catalyzed by Dimethylallyltryptophan Synthase?

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 e...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 133; no. 32; pp. 12342 - 12345
Main Authors Luk, Louis Y. P, Qian, Qi, Tanner, Martin E
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 17.08.2011
Subjects
Alkyl and Aryl Transferases - genetics
Alkyl and Aryl Transferases - metabolism
Aspergillus fumigatus - enzymology
Aspergillus fumigatus - genetics
Indole Alkaloids - metabolism
Mutagenesis, Site-Directed
Prenylation
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Summary: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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ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/ja2034969