Journal article

Authors list: Graulich, N

Publication year: 2011

Pages: 172-190

Journal: WIREs: Computational Molecular Science

Volume number: 1

Issue number: 2

ISSN: 1759-0876

DOI Link: https://doi.org/10.1002/wcms.17

Publisher: Wiley

Abstract: 
This review takes the experimental and theoretical discussions on the Cope rearrangement as the basis to emphasize its tight connection to many closely related pericyclic reactions. The Cope reaction, which is rather simple in a formal sense, has led to a plethora of mechanistic discussions to determine the nature of biradical-like intermediates or transition structures. After intense experimental and theoretical investigations starting in the late 1960s, the Cope rearrangement turned out to be a multifaceted reaction with a 'chameleonic' nature, ranging from homoaromatic transition structures to biradical intermediates in substituted cases, and six-electron transition states in the parent system. Additionally, the Cope rearrangement served as an excellent example to probe theoretical methods for the computations of a variety of pericyclic reactions. However, the relationship of the Cope rearrangement with analogous reactions has been hampered by the notion that pericyclic reactions typically are assumed to proceed in a concerted fashion. Only in the past 10 years, the Cope reaction, with its 1,5-hexadiene unit, emerged as the structural and mechanistic prototype of a large family, including sigmatropic, cycloaddition, and other electrocyclic reactions as well as thermal rearrangements of polyunsaturated systems, enediynes, eneyneallenes, and many others. The recurrent and interconnecting motif in this family of reactions is the questions regarding cyclic aromatic transition states and the possible involvement of biradical intermediates.

Harvard Citation style: Graulich, N. (2011) The Cope rearrangement - the first born of a great family, WIREs: Computational Molecular Science, 1(2), pp. 172-190. https://doi.org/10.1002/wcms.17

APA Citation style: Graulich, N. (2011). The Cope rearrangement - the first born of a great family. WIREs: Computational Molecular Science. 1(2), 172-190. https://doi.org/10.1002/wcms.17