Substituent Effects on Temperature Dependence of Kinetic Isotope Effects in Hydride-Transfer Reactions of NADH/NAD + Analogues in Solution: Reaction Center Rigidity Is the Key
Substituent Effects on Temperature Dependence of Kinetic Isotope Effects in Hydride-Transfer Reactions of NADH/NAD + Analogues in Solution: Reaction Center Rigidity Is the Key
复制标题
溶液中 NADH/NAD 类似物氢化物转移反应中取代基对动力学同位素效应温度依赖性的影响：反应中心刚性是关键
DOI：
10.1021/acs.orglett.0c02049
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发表时间：
2020
期刊：
影响因子：
5.2
通讯作者：
Lu, Yun
中科院分区：
文献类型：
--
作者：
Maness, Peter;Koirala, Shailendra;Adhikari, Pratichhya;Salimraftar, Nasim;Lu, Yun
本文研究了乙腈中两个系列的标题反应的取代基效应对初级动力学同位素效应的温度依赖性，其特征为ΔEa=EaD-EaH。观察到从高刚性系统的ΔEa> 0到刚性降低系统的ΔEa> 0的变化。刚性由电子效应和空间效应控制。这项工作复制了酶中的观察结果，并开辟了一个新的研究方向，研究结构-Δ E关系。
Substituent effects on the temperature dependence of primary kinetic isotope effects, characterized by ΔEa=EaD–EaH, for two series of the title reactions in acetonitrile were studied. The change from ΔEa≈ 0 for a highly rigid system to ΔEa> 0 for systems with reduced rigidities was observed. The rigidities were controlled by the electronic and steric effects. This work replicates the observations in enzymes and opens a new research direction that studies structure−ΔEarelationship.