使用大体积铵自由基的无导向基团芳烃C(sp)-H胺化反应及区域选择性的密度泛函理论分析
Directing-Group-Free Arene C(sp)-H Amination Using Bulky Aminium Radicals and DFT Analysis of Regioselectivity.
作者信息
Behnke Nicole Erin, Kwon Young-Do, Davenport Michael T, Ess Daniel H, Kürti László
机构信息
Department of Chemistry, Rice University, Houston, Texas 77030, United States.
Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, United States.
出版信息
J Org Chem. 2023 Aug 18;88(16):11847-11854. doi: 10.1021/acs.joc.3c01127. Epub 2023 Jul 28.
Abstract
A hydroxylamine-derived electrophilic aminating reagent produces a transient and bulky aminium radical intermediate upon activation by either TMSOTf or TFA and a subsequent electron transfer from an iron(II) catalyst. Density functional theory calculations were used to examine the regioselectivity of arene C-H amination reactions on diversely substituted arenes. The calculations suggest a simple charge-controlled regioselectivity model that enables prediction of the major C(sp)-H amination product.
摘要
一种源自羟胺的亲电胺化试剂在被三甲基甲磺酸三氟甲酯（TMSOTf）或三氟乙酸（TFA）活化以及随后从铁（II）催化剂进行电子转移时会产生一种瞬态且体积较大的铵基自由基中间体。密度泛函理论计算被用于研究在不同取代芳烃上芳烃C-H胺化反应的区域选择性。这些计算表明了一种简单的电荷控制区域选择性模型，该模型能够预测主要的C(sp)-H胺化产物。
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