Tomiczek Breanna M, Grenning Alexander J
Department of Chemistry, University of Florida, PO Box 117200, Gainesville, FL, USA.
Org Biomol Chem. 2021 Mar 21;19(11):2385-2398. doi: 10.1039/d1ob00094b. Epub 2021 Mar 2.
Reviewed herein is the aromatic Cope rearrangement, a Cope rearrangement where one (or both) of the alkenes of the 1,5-diene are part of a greater aromatic system. While the Cope rearrangement of 1,5-dienes has seen wide utility, variation, and application in chemical synthesis, the aromatic Cope rearrangement, comparatively, has not. This review summarizes the ∼40 papers dating back to 1956 on this topic and is divided into the following sections: (1) introduction, including kinetic and thermodynamic challenges of the aromatic Cope rearrangement, and (2) key substrate features, of which there are four general types: (i) α-allyl-α-aryl malonates (and related substrates), (ii) 1-aryl-2-vinylcyclopropanes, and (iii) anion-accelerated aromatic oxy-Cope substrates, and (iv) the concept of synchronized aromaticity. Ultimately, we hope this review will draw attention to a potentially valuable transformation for arene functionalization that warrants further studies and development.
本文综述了芳香族科普重排反应，即在1,5 - 二烯中，其中一个（或两个）烯烃是更大芳香体系的一部分的科普重排反应。虽然1,5 - 二烯的科普重排反应在化学合成中具有广泛的用途、变化形式和应用，但相比之下，芳香族科普重排反应却并非如此。本综述总结了自1956年以来关于该主题的约40篇论文，并分为以下几个部分：（1）引言，包括芳香族科普重排反应的动力学和热力学挑战；（2）关键底物特征，共有四种常见类型：（i）α - 烯丙基-α - 芳基丙二酸酯（及相关底物），（ii）1 - 芳基 - 2 - 乙烯基环丙烷，（iii）阴离子加速的芳香族氧基科普底物，以及（iv）同步芳香性的概念。最终，我们希望本综述能引起人们对一种可能有价值的芳烃官能化转化反应的关注，该反应值得进一步研究和开发。
