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Chiral‐Substrate‐Assisted Stereoselective Epoxidation Catalyzed by H 2 O 2 ‐Dependent Cytochrome P450 SPα
Author(s) -
Fujishiro Takashi,
Shoji Osami,
Kawakami Norifumi,
Watanabe Takahiro,
Sugimoto Hiroshi,
Shiro Yoshitsugu,
Watanabe Yoshihito
Publication year - 2012
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201200250
Subject(s) - styrene oxide , styrene , stereoselectivity , chemistry , chirality (physics) , molecule , catalysis , stereochemistry , organic chemistry , copolymer , polymer , chiral symmetry , physics , quantum mechanics , nambu–jona lasinio model , quark
The stereoselective epoxidation of styrene was catalyzed by H 2 O 2 ‐dependent cytochrome P450 SPα in the presence of carboxylic acids as decoy molecules. The stereoselectivity of styrene oxide could be altered by the nature of the decoy molecules. In particular, the chirality at the α‐positions of the decoy molecules induced a clear difference in the chirality of the product: ( R )‐ibuprofen enhanced the formation of ( S )‐styrene oxide, whereas ( S )‐ibuprofen preferentially afforded ( R )‐styrene oxide. The crystal structure of an ( R )‐ibuprofen‐bound cytochrome P450 SPα (resolution 1.9 Å) revealed that the carboxylate group of ( R )‐ibuprofen served as an acid–base catalyst to initiate the epoxidation. A docking simulation of the binding of styrene in the active site of the ( R )‐ibuprofen‐bound form suggested that the orientation of the vinyl group of styrene in the active site agreed with the formation of ( S )‐styrene oxide.