Pellegrinet Silvina C, Goodman Jonathan M
Instituto de Química Organica y de Síntesis (CONICET), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, Rosario (2000), Argentina.
J Am Chem Soc. 2006 Mar 15;128(10):3116-7. doi: 10.1021/ja056727a.
The conjugate addition of alkynylboronates to enones catalyzed by binaphthols has been studied theoretically with DFT methods. The high reactivity of the alkynylboronate derived from binaphthol seems to arise from electronic effects since its acidic boron atom binds tightly to the enone carbonyl and lowers the activation energy of the alkynylboration step. Steric clashes between the atoms of the ligands on boron and the enone can be invoked to account for the observed facial diastereoselectivity. The competing hetero-Diels-Alder reactions are computed to be kinetically disfavored relative to alkynylborations.
利用密度泛函理论（DFT）方法对联萘酚催化的烯炔硼酸酯与烯酮的共轭加成反应进行了理论研究。源自联萘酚的烯炔硼酸酯的高反应活性似乎源于电子效应，因为其酸性硼原子与烯酮羰基紧密结合，降低了烯炔硼化步骤的活化能。硼上配体的原子与烯酮之间的空间冲突可用于解释所观察到的面式非对映选择性。计算结果表明，相对于烯炔硼化反应，竞争性的杂环狄尔斯-阿尔德反应在动力学上是不利的。
