Stereoelectronic requirements for optimal hydrogen-bond-catalyzed enolization

Pápai I.; Hamza A.; Pihko P.M.; Wierenga R.K.

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Stereoelectronic requirements for optimal hydrogen-bond-catalyzed enolization

机译：最佳氢键催化烯化的立体电子要求

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摘要

Protein crystallographic analysis of the active sites of enolizing enzymes and structural analysis of hydrogen-bonded carbonyl compounds in small molecule crystal structures, complemented by quantum chemical calculations on related model enolization reactions, suggest a new stereoelectronic model that accounts for the observed out-of-plane orientation of hydrogen-bond donors (HBDs) in the oxyanion holes of enolizing enzymes. The computational results reveal that the lone-pair directionality of HBDs characteristic for hydrogen-bonded carbonyls is reduced upon enolization, and the enolate displays almost no directional preference for hydrogen bonding. Positioning the HBDs perpendicular to the carbonyl plane induces strain in the catalyst-substrate complex, which is released upon enolization, resulting in more favorable kinetics and thermodynamics than the in-plane arrangement of HBDs.

机译：蛋白质结晶分析的活性位点，其雄性晶体结构中的氢键碳基化合物的结构分析，由量子化学计算对相关模型烯化反应的补充，提出了一种新的立体电子模型，其占观察到的 - 氢键供体（HBDS）在氧化酶的氧基孔中的平面取向。计算结果表明，在钠化时降低了氢键碳基的HBDS特性的孤立型方向性，并且烯醇烯几乎没有用于氢键的方向偏好。将HBDS定位在羰基面上诱导催化剂 - 底物复合物的菌株，该催化剂 - 底物复合物在烯化时被释放，导致比HBD的面内排列更有利的动力学和热力学。

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《Chemistry: A European journal》 |2011年第10期|共8页
作者
Pápai I.; Hamza A.; Pihko P.M.; Wierenga R.K.;
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作者单位

Department of Theoretical Chemistry Chemical Research Center Hungarian Academy of Sciences Pusztaszeri ut 59-67 H-1025 Budapest Hungary;

Department of Theoretical Chemistry Chemical Research Center Hungarian Academy of Sciences Pusztaszeri ut 59-67 H-1025 Budapest Hungary;

Department of Chemistry University of Jyv?skyl? FI-40014 JYU Finland;

Biocenter Oulu and Department of Biochemistry University of Oulu Box 3000 FI-90014 Finland;

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原文格式 PDF
正文语种 eng
中图分类应用化学;
关键词
catalyst design; density functional theory; enolization; hydrogen bonds; oxyanion hole;

机译：催化剂设计;密度函数理论;雄结;氢键;氧气孔;

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机译：木瓜蛋白酶与底物衍生的重氮甲基酮反应的机理暗示了卤甲基酮对丝氨酸蛋白酶和半胱氨酸蛋白酶的位点特异性的差异以及木瓜蛋白酶催化机理的立体电子学要求
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机译：木瓜蛋白酶与底物衍生的重氮甲基酮反应的机理暗示了卤甲基酮对丝氨酸蛋白酶和半胱氨酸蛋白酶的位点特异性的差异以及木瓜蛋白酶催化机理的立体电子学要求

Stereoelectronic requirements for optimal hydrogen-bond-catalyzed enolization

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