Mechanistic Study of the Stereoselective Hydroxylation of [2-2 H1 ,3-2 H1 ]Butanes Catalyzed by Cytochrome P450 BM3 Variants.
作者： Chung-Ling Yang , Cheng-Hung Lin , Wen-I Luo , Tsu-Lin Lee , Ravirala Ramu
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摘要: Engineered bacterial cytochrome P450s are noted for their ability in the oxidation of inert small alkanes. Cytochrome P450 BM3 L188P A328F (BM3 PF) and A74E EPF) variants able to efficiently oxidize n-butane 2-butanol. Esterification 2-butanol derived from this reaction mediated by aforementioned two mutants gives diastereomeric excess (de) -56±1 -52±1%, respectively, with preference occurred at C-HS bond. Interestingly, when tailored (2R,3R)- (2S,3S)-[2-²H₁,3-²H₁]butanes employed as substrates both variants, obtained de (2R,3R)-[2-²H₁,3-²H₁]butane -93 -92% PF EPF systems, respectively; whereas (2S,3S)-[2-²H₁,3-²H₁]butane 52 56% respectively. The kinetic isotope effects (KIEs) 7.3 7.8 KIEs 18 25 discrepancy supports two-state reactivity (TSR) that is proposed alkane system. Moreover, first time, experimental evidence tunneling given through C-HR bond on (2S,3S)-[2-²H₁,3-²H₁]butane.
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