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Chemically Unprecedented Biocatalytic (AuaG) Retro‐[2,3]‐Wittig Rearrangement: A New Insight into Aurachin B Biosynthesis
Author(s) -
Katsuyama Yohei,
Li XuWen,
Müller Rolf,
Nay Bastien
Publication year - 2014
Publication title -
chembiochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.05
H-Index - 126
eISSN - 1439-7633
pISSN - 1439-4227
DOI - 10.1002/cbic.201402373
Subject(s) - biosynthesis , biocatalysis , wittig reaction , chemistry , stereochemistry , catalysis , enzyme , combinatorial chemistry , organic chemistry , reaction mechanism
Abstract AuaG is flavin‐dependent monooxygenase responsible for the conversion of aurachin C to aurachin B, a reaction thought to resemble semipinacol migration of the farnesyl substituent. A study of the substrate tolerance of AuaG reveals that it has the peculiar ability to oxidise short‐chain analogues of aurachin D. Unexpectedly, a novel retro‐[2,3]‐Wittig rearrangement was observed with an isoprenyl substrate analogue, thus leading to the 1,1‐dimethylallyl ether. Additionally, we found that saturated‐chain analogues of N‐oxidised aurachin C were not transformed by the C3→C4 semipinacol reaction, as might have been expected for such substrates. Based on this and the unique retro‐[2,3]‐Wittig rearrangement, we discuss an alternative biosynthetic route for the conversion of aurachin C to aurachin B.