Alder-ene reaction: Aromaticity and activation-strain analysis
Alder-ene reaction: Aromaticity and activation-strain analysis
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DOI：
10.1002/jcc.22877
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发表时间：
2012-02-15
影响因子：
3
通讯作者：
Bickelhaupt, F. Matthias
中科院分区：
文献类型：
--
作者：
Fernandez, Israel;Bickelhaupt, F. Matthias
本文利用密度泛函理论，在M06-2X/def2-TZVPP下，计算探讨了丙烯与一系列7种亲和试剂之间醛烯反应的反应活性趋势。反应势垒沿亲亲和试剂的顺序递减，依次为H2C？Ch2 > hc ？ch> h2c ？Nh > h2c ？Ch (cooch3) > h2c ？O > h2c ？Ph > h2c ? s。因此，当第三周期原子参与到亲亲和试剂的双键中时，势垒的下降尤为明显。活化应变分析表明，反应性的这种趋势与反应物从平衡结构变形到过渡态的几何形状所引起的活化应变有关。我们讨论了这一趋势的起源，以及它与氢从烯向亲亲和物转移和新C？C键。(c) 2011 Wiley期刊公司计算机学报，2011
We have computationally explored the trend in reactivity of the Alder-ene reactions between propene and a series of seven enophiles using density functional theory at M06-2X/def2-TZVPP. The reaction barrier decreases along the enophiles in the order H2C?CH2 > HC?CH > H2C?NH > H2C?CH(COOCH3) > H2C?O > H2C?PH > H2C?S. Thus, barriers drop in particular, if third-period atoms become involved in the double bond of the enophile. Activation-strain analyses show that this trend in reactivity correlates with the activation strain associated with deforming reactants from their equilibrium structure to the geometry they adopt in the transition state. We discuss the origin of this trend and its relationship with the extent of synchronicity between H transfer from ene to enophile and the formation of the new C?C bond. (c) 2011 Wiley Periodicals, Inc. J Comput Chem, 2011