NDLI: Tuning the Regio- and Stereoselectivity of CH Activation in n-Octanes by Cytochrome P450 BM-3 with Fluorine Substituents: Evidence for Interactions Between a CF Bond and Aromatic π Systems

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Tuning the Regio- and Stereoselectivity of CH Activation in n-Octanes by Cytochrome P450 BM-3 with Fluorine Substituents: Evidence for Interactions Between a CF Bond and Aromatic π Systems

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Chang, Chun-wei Chou, Ho-hsuan Lo, Feng-chun Yang, Chung-ling Chiang, Chih-hsiang Ng, Kok Yaoh Hung, Huei-ying Chan, Sunney I. Yu, Steve S-f Wu, Li-lan
Description	Author Affiliation: Wu LL ( Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan.)
Abstract	We employed the water- soluble cytochrome P450 BM-3 to study the activity and regiospecificity of oxidation of fluorinated n-octanes. Three mutations, A74G, F87V, and L188Q, were introduced into P450 BM-3 to allow the system to undergo n-octane oxidation. In addition, the alanine at residue 328 was replaced with a phenylalanine to introduce an aromatic residue into the hydrophobic pocket to examine whether or not van der Waals interactions between a CF substituent in the substrate and the polarizable π system of the phenylalanine may be used to steer the positioning of the substrate within the active-site pocket of the enzyme and control the regioselectivity and stereoselectivity of hydroxylation. Interestingly, not only was the regioselectivity controlled when the fluorine substituent was judiciously positioned in the substrate, but the electron input into the iron–heme group became tightly coupled to the formation of product, essentially without abortive side reactions. Remarkable enhancement of the coupling efficiency between electron input and product formation was observed for a range of fluorinated octanes in the enzyme even without the A328F mutation, presumably because of interactions of the CF substituent with the π system of the porphyrin macrocycle within the active-site pocket. Evidently, tightening the protein domain containing the heme pocket tunes the distribution of accessible enzyme conformations and the associated protein dynamics that activate the iron porphyrin for substrate hydroxylation to allow the reactions mediated by the high-valent $Fe^{IV}O$ to become kinetically more commensurate with electron transfer from the flavin adenine dinucleotide (FAD)/flavin mononucleotide (FMN) reductase. These observations lend compelling evidence to support significant van der Waals interactions between the $CF_{2}$ group and aromatic π systems within the heme pocket when the fluorinated octane substrate is bound.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	17
Volume Number	17
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2011-04-18
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Cytochrome P-450 Enzyme System Chemistry Flavin Mononucleotide Flavin-Adenine Dinucleotide Fluorine Hydrocarbons, Fluorinated Octanes Electron Transport Hydrogen Bonding Hydroxylation Molecular Conformation Mutagenesis Oxidation-Reduction Solubility Stereoisomerism Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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