Computational Study with DFT and Kinetic Models on the Mechanism of Photoinitiated Aromatic Perfluoroalkylations
Computational Study with DFT and Kinetic Models on the Mechanism of Photoinitiated Aromatic Perfluoroalkylations
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DOI：
10.1021/acs.orglett.5b01069
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发表时间：
2015-06-05
期刊：
影响因子：
5.2
通讯作者：
Maseras, Feliu
中科院分区：
文献类型：
--
作者：
Fernandez-Alvarez, Victor M.;Nappi, Manuel;Maseras, Feliu
DFT计算和动力学模型的组合，充分阐明了看似复杂的反应性α-氰基芳基乙酸对无金属光引发芳族全氟烷基化。由此产生的机制框架合理化所观察到的量子产率，以及在反应性和/或选择性的差异，看似相似的基板。动力学模型的DFT计算的反应常数的化学解释的使用被证明是至关重要的。
A combination of DFT calculations and kinetic models is applied to fully elucidate the seemingly complex reactivity of alpha-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.