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Reverse versus Normal Prenyl Transferases in Paraherquamide Biosynthesis Exhibit Distinct Facial Selectivities
Author(s) -
Stocking Emily M.,
SanzCervera Juan F.,
Williams Robert M.
Publication year - 1999
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/(sici)1521-3773(19990315)38:6<786::aid-anie786>3.0.co;2-7
Subject(s) - isoprene , prenylation , moiety , stereochemistry , biosynthesis , chemistry , transferase , biochemistry , enzyme , organic chemistry , copolymer , polymer
Both a face‐selective and a non‐face‐selective mode of formation of quaternary centers of isoprene‐derived structural moieties of the natural alkaloid paraherquamide A ( 1 ) have been discovered by feeding experiments on Penicillium fellutanum with [U‐ 13 C 6 ]‐glucose and [ 13 C 2 ]‐acetate. The labeling patterns suggest that the methyl groups (C22, C23) are introduced in a non‐face‐selective manner by a reverse prenyl transferase. The C 5 unit comprising the dioxepin moiety retains stereochemical integrity indicative of a single, face‐selective addition of the phenolic group to the dimethylallyl group.