Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages
Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages
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DOI：
10.1021/jacs.2c04179
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发表时间：
2022-06-14
影响因子：
15
通讯作者：
Tantillo, Dean J.
中科院分区：
文献类型：
--
作者：
Quynh Nhu N Nguyen;Xia, Kay T.;Tantillo, Dean J.
量子化学和分子动力学计算的结果表明，聚阴离子镓基笼加速环化反应的底物笼的相互作用，优先结合的反应构象的基板/H3O+对，并增加基板的碱性的结果醇。然而，碱度的增加占主导地位。实验结构活性关系的研究，其中的金属顶点和总电荷的笼是不同的确认通过计算得出的模型。
The results of quantum chemical and molecular dynamics calculations reveal that polyanionic gallium-based cages accelerate cyclization reactions of pentadienyl alcohols as a result of substrate cage interactions, preferential binding of reactive conformations of substrate/H3O+ pairs, and increased substrate basicity. However, the increase in basicity dominates. Experimental structure-activity relationship studies in which the metal vertices and overall charge of the cage are varied confirm the model derived via calculations.