Divinylcyclopropane-Cycloheptadiene Rearrangement

Hudlicky´, Tomásˇ; Fan, Rulin; Reed, Josephine W.; Gadamasetti, Kumar G.


The first documented report of a possible Cope rearrangement was probably that of Baeyer, who prepared eucarvone by hydrobromination of carvone in 1894. Although the transformation was briefly studied at that time, it was not until the 1950s that this and other Cope-type rearrangements received detailed attention. The thermal isomerization of cis-divinylcyclopropane to cycloheptan-1,4-diene was reported by Vogel in 1960 during his studies of the Cope rearrangement of 1,5-hexadienes annulated by a homologous series of carbocyclic rings. Scores of mechanistic studies followed this discovery upon the realization that the rearrangement could be related to the conceptually similar vinylcyclopropane–cyclopentene isomerization discovered a year earlier. It was also recognized that this rearrangement might be operating in the formation of cycloheptatriene from norcaradiene during photolysis of diazomethane in benzene. The topic received considerable attention in the 1960s, an era of mechanistic investigations of various concerted transformations. During the 1970s it enjoyed exploitation in many synthetic strategies, and the following decade the elements of this rearrangement were incorporated into tandem or multistep procedures in a preconceived manner. Many aspects of the various permutations of the Cope rearrangement have been previously reviewed.

The purpose of this review is to summarize the mechanistic, stereochemical, and practical results in this area in the context of the evolution of synthetic achievements during the last 40 years. Also described in this chapter are the transformations of several of the simple heteroatom permutations of this rearrangement in order to render appropriate comparisons of various systems. A discussion addresses those rearrangements of cyclopropanes, oxiranes, thiiranes, and aziridine rings substituted with vicinal vinyl groups. Excluded from this review are rearrangements of those divinylsubstituted three-membered rings that contain more than a single heteroatom within the reacting manifold. Brief mention of these systems along with a guide to the literature is found in the last section of this chapter.

The literature is covered through December 1990. Many of the principal researchers in this field have been contacted and many unpublished transformations have been included in the tables.