Aromatic Cope rearrangements

Abstract

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.