Case for Lithium Tetramethylpiperidide-Mediated Ortholithiations: Reactivity and Mechanisms.
Case for Lithium Tetramethylpiperidide-Mediated Ortholithiations: Reactivity and Mechanisms.
复制标题
四甲基哌啶锂介导的正锂化案例：反应性和机制。
DOI：
10.1021/jacs.8b00590
复制
发表时间：
2018
影响因子：
15
通讯作者：
Collum,DavidB
中科院分区：
文献类型：
--
作者：
Mack,KyleA;Collum,DavidB
2,2,6,6-四甲基哌啶锂的邻锂化速率和机理研究集中在四种芳烃上：1,4-双(三氟甲基)苯、1,3-双(三氟甲基)苯、1,3-二甲氧基苯和4,4-二甲基-2-苯基-2-恶唑啉。金属化通过单溶剂化单体、溶解单体和四溶剂化二聚体（三离子）的底物依赖性组合发生。密度泛函理论计算研究增强了实验数据。我们讨论了在确定可观察的反应级数时改变二聚体-单体比例所带来的挑战，以及我们对反应物结构中这种变化的数学处理。
Rate and mechanistic studies of ortholithiations by lithium 2,2,6,6-tetramethylpiperidide focus on four arenes: 1,4-bis(trifluoromethyl)benzene, 1,3-bis(trifluoromethyl)benzene, 1,3-dimethoxybenzene, and 4,4-dimethyl-2-phenyl-2-oxazoline. Metalations occur via substrate-dependent combinations of monosolvated monomer, disolvated monomer, and tetrasolvated dimer (triple ions). Density functional theory computational studies augment the experimental data. We discuss the challenges presented by shifting dimer–monomer proportions in determining the observable reaction orders and our mathematical treatment of such shifting in reactant structure.