From Discovery to Application: 50 Years of the Vinylcyclopropane–Cyclopentene Rearrangement and Its Impact on the Synthesis of Natural Products

Abstract

A classic that hasn't lost its charm: The historical origins and current status of the vinylcyclopropane–cyclopentene rearrangement and the corresponding transformations of heteroatom‐containing analogues (see scheme) are described in the context of methodology development and natural products synthesis. Several important events that greatly influenced the author's own research program some 30 to 40 years ago are recounted as personal recollections.

Recent applications of the divinylcyclopropane–cycloheptadiene rearrangement in organic synthesis

“…The resulting vinyl-epoxide ketone underwent rearrangement to give dihydrooxepine 310 in good yield. Vinylcyclopropane–cyclopentene rearrangement [13–14] has been shown to be the major competing side reaction in this case.…”

“…The Buchner ring expansion [11–12] as a special case of the DVCPR is not part of this review. The related vinylcylopropane–cyclopentene rearrangement has been reviewed elsewhere [13–14]. …”

Intraannular photoreactions in pseudo-geminally substituted [2.2]paracyclophanes

“…Whereas this Z → E- isomerization process must involve a diradical intermediate of type 17 , its lifetime is evidently too short to allow ring-expansion as depicted in Scheme 7. Whether this process might be induced thermally (vinylcyclopropane→cyclopentene rearrangement; [23]) is an open question.…”

Cobalt‐Catalyzed Diastereo‐ and Enantioselective Hydroalkenylation of Cyclopropenes with Alkenylboronic Acids

“…Alkenylcyclopropanes are important building blocks in organic synthesis,w ell known to participate in various rearrangement reactions [1] and transition metal catalyzed cyclizations to access polycyclic molecular structures of high complexity. [2] In addition, such entities also commonly exist in biologically active natural products and pharmaceutically important molecules ( Figure 1).…”