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首页> 外文期刊>Chemistry: A European journal >Mechanistic Study of the Stereoselective Hydroxylation of [2-~2H1,3-~2H1]Butanes Catalyzed by Cytochrome P450 BM3 Variants
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Mechanistic Study of the Stereoselective Hydroxylation of [2-~2H1,3-~2H1]Butanes Catalyzed by Cytochrome P450 BM3 Variants

机译：通过细胞色素P450 BM3变体催化催化羟基的机械研究[2-〜2H1,3-〜2H1]丁烷丁烷

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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 L188P A328F (BM3 EPF) variants are able to efficiently oxidize nbutane to 2-butanol. Esterification of the 2-butanol derived from this reaction mediated by the aforementioned two mutants gives diastereomeric excesses (de) of -56±1 and -52±1%, respectively, with the preference for the oxidation occurring at the C-H_S bond. When tailored (2R,3R)- and (2S,3S)-[2-~2H_1,3-~2H_1]butane probes are employed as substrates for both variants, the obtained de values from (2R,3R)-[2-~2H_1,3-~2H_1]butane are -93 and -92% for BM3 PF and EPF, respectively; whereas the obtained de values from (2S,3S)-[2-~2H_1,3-~2H_1]butane are 52 and 56% in the BM3 PF and EPF systems, respectively. The kinetic isotope effects (KIEs) for the oxidation of (2R,3R)-[2-~2H_1,3-~2H_1]butane are 7.3 and 7.8 in BM3 PF and EPF, respectively; whereas KIEs for (2S,3S)-[2-~2H_1,3-~2H_1]butanes are 18 and 25 in BM3 PF and EPF, respectively. The discrepancy in KIEs obtained from the two substrates supports the two-state reactivity (TSR) that is proposed for alkane oxidation in cytochrome P450 systems. Moreover, for the first time, experimental evidence for tunneling in the oxidation mediated by P450 is given through the oxidation of the C-H_R bond in (2S,3S)-[2-~2H_1,3- ~2H_1]butane.
机译：注读工程化细菌细胞色素P450s在惰性小烷烃氧化中的能力。细胞色素P450 BM3 L188P A328F（BM3 PF）和A74E L188P A328F（BM3 EPF）变体能够有效地将Nbutane氧化为2-丁醇。由上述两个突变体介导的该反应介导的2-丁醇的酯化分别介导的两种突变体分别为-56±1和-52±1％的非对映异构体过量（DE），优选在C-H键处发生氧化。当定制（2R，3R） - 和（2S，3S） - [2-〜2H_1,3-〜2H_1]丁烷探针作为两个变体的底物，所获得的DE值（2R，3R） - [2- 〜2H_1,3-〜2H_1]丁烷分别为-93和-92％，分别为BM3 PF和EPF;从（2S，3S） - [2-〜2H_1,3-〜2H_1]丁烷中获得的DE值分别分别为BM3 PF和EPF系统中的52和56％。用于氧化的动力学同位素效应（2R，3R） - [2-〜2H_1,3-〜2H_1]丁烷分别为BM3 PF和EPF的7.3和7.8;虽然（2S，3S） - [2-〜2H_1,3-〜2H_1]丁烷分别为18和25，分别为BM3 PF和EPF。从两个基板获得的kies中的差异支持在细胞色素P450系统中提出用于烷烃氧化的两个状态反应性（TSR）。此外，首次，通过（2S，3S） - [2-〜2H_1,3-〜2H_1]丁烷的C-H_R键氧化，给出P450介导的氧化在氧化中的渗透的实验证据。

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