Density functional theory study of a Lewis acid catalyzed Diels-Alder reaction.: The butadiene plus acrolein paradigm
Density functional theory study of a Lewis acid catalyzed Diels-Alder reaction.: The butadiene plus acrolein paradigm
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DOI：
10.1021/ja9722279
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发表时间：
1998-03-18
影响因子：
15
通讯作者：
Salvatella, L
中科院分区：
文献类型：
--
作者：
García, JI;Martínez-Merino, V;Salvatella, L
利用DFT （B3LYP）计算方法，从理论上研究了丁二烯与丙烯醛反应的四种过渡结构（TS's），包括非催化和BF3催化的反应。在非催化反应和催化反应中，末端s顺式是四种可能的过渡结构中最稳定的。在催化反应的情况下，在寻找这种过渡结构时包含电子关联表明，经典的[4+2]反应路径，而不是[2+4]逆电子对应的反应路径，需要异源diols - alder反应，正如使用理论的Hartree-Fock能级时所发生的那样。B3LYP/6-31G(d)计算得到的活化能值与实验结果接近。讨论了在催化剂存在和不存在的情况下内/外选择性的来源。
The four transition structures (TS's) of the reaction between butadiene and acrolein, both uncatalyzed and catalyzed by BF3, have been theoretically studied taking into account electron correlation effects by means of DFT (B3LYP) calculations. In both the uncatalyzed and catalyzed reactions, the endo s-cis is the most stable of the four possible transition structures. In the case of the catalyzed reaction, the inclusion of electron correlation in the search for this transition structure indicates the classical [4+2] reaction path, instead of that corresponding to a [2+4] inverse electron, demands hetero-Diels-Alder reaction, as happens when the Hartree-Fock level of theory is used. The B3LYP/6-31G(d) calculations lead to activation energy values close to those experimentally found. The origin of the endo/exo selectivity, both in the presence and in the absence of the catalyst, is discussed.