Fernández-Alvarez Victor M, Nappi Manuel, Melchiorre Paolo, Maseras Feliu
†Institute of Chemical Research of Catalonia (ICIQ), Avgda. Països Catalans 16, 43007 Tarragona, Catalonia, Spain.
‡Institució Catalana de Recerca i Estudis Avançats, Passeig Lluís Companys 23, 08010 Barcelona, Spain.
Org Lett. 2015 Jun 5;17(11):2676-9. doi: 10.1021/acs.orglett.5b01069. Epub 2015 May 14.
A combination of DFT calculations and kinetic models is applied to fully elucidate the seemingly complex reactivity of α-cyano arylacetates toward metal-free photoinitiated aromatic perfluoroalkylation. The resulting mechanistic framework rationalizes the observed quantum yield as well as the differences in reactivity and/or selectivity of seemingly similar substrates. The use of a kinetic model for the chemical interpretation of the DFT-computed reaction constants is shown to be critical.
采用密度泛函理论（DFT）计算和动力学模型相结合的方法，以全面阐明α-氰基芳基乙酸酯对无金属光引发芳族全氟烷基化反应看似复杂的反应活性。所得的机理框架解释了观察到的量子产率以及看似相似底物在反应活性和/或选择性上的差异。结果表明，使用动力学模型对DFT计算的反应常数进行化学解释至关重要。
