Department of Chemistry , Radford University , Radford , Virginia 24142 , United States.
Department of Chemistry , Virginia Polytechnic University , Blacksburg , Virginia 24061 , United States.
J Phys Chem A. 2019 Nov 7;123(44):9450-9455. doi: 10.1021/acs.jpca.9b06413. Epub 2019 Sep 30.
Pentafluoropyridine, a potentially useful precursor in organofluorine methodology, undergoes selective substitution of a fluorine with a phenoxide at the site to the nitrogen. Subsequent aryloxide substitutions can be accomplished at the -positions with aryloxide groups containing various functional groups to the phenoxide oxygen. During this phase of the reaction, "reverse reactions" involving substitutions of the original substituent with a free fluoride or with another aryloxide moiety are observed with a frequency that depends on the functional group to the oxygen on the aryloxide. Herein, we provide a theoretical explanation of these observations through use of density functional theory.
五氟吡啶是有机氟化学方法中一种很有前途的前体，它在氮原子邻位选择性地被酚氧基取代一个氟原子。随后，在邻位可以用含有各种官能团的酚氧基取代基进行芳氧基取代。在反应的这一阶段，观察到涉及用游离氟或另一个芳氧基部分取代原始取代基的“逆反应”，其频率取决于芳氧基上氧原子的官能团。在此，我们通过使用密度泛函理论对这些观察结果进行了理论解释。
