化学选择性
化学
催化作用
超分子化学
选择性
超分子催化
位阻效应
反应性(心理学)
反应机理
过渡状态
普林斯反应
非共价相互作用
光化学
组合化学
计算化学
立体化学
有机化学
分子
氢键
医学
替代医学
病理
作者
Na Li,Qian Wang,Shuping Zhuo,Li‐Ping Xu
标识
DOI:10.1021/acscatal.3c02756
摘要
The mechanism, reactivity, and selectivity of the aza-Prins reaction in both the bulk solution and under [Ga4L6]12- (L = N,N-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene) supramolecular catalysis were studied by means of theoretical calculations. In bulk solution, the steric effect and donor–acceptor interaction which favor the parallel-conformation transition state, in the selectivity-determining cyclization step, account for the observed chemoselectivity that leads to the alcohol product. While under the [Ga4L6]12– catalysis, the host–guest noncovalent interaction and confinement effect are more critical and make the vertical-conformation transition state more favorable, i.e., switch the chemoselectivity of the reaction that leads to the piperidine product. The presented calculations explain the reactivities of substrates by the cavity size-determined guest recognition. The computational findings are in good agreement with experiment. This work sheds light on development of more efficient and selective supramolecular catalysis.
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