Divergent Rearrangements of Vinylcyclopropane into Skipped Diene and Cyclopentene: Mechanism, Scope, and Limitations

Vinylcyclopropanes are versatile intermediates in organic synthesis which undergo various rearrangements. We report a new rearrangement of vinylcyclopropane into skipped diene. A detailed mechanistic study revealed that this transformation involves regioselective ring-opening of the cyclopropane ring followed by 1,2-migration of one of the cyclopropane substituents. Interestingly, our investigations showed that skipped diene is the kinetic product of the process but formation of a more stable cyclopentene is also accessible. The fundamental understanding of the processes involved enabled the development of divergent methodologies allowing to obtain cyclopentene or skipped diene from vinylcyclopropane in a selective and controlled manner.

Automated summary

A new rearrangement of vinylcyclopropane into skipped diene was reported, involving regioselective ring-opening and migration of substituents. The kinetic product of the process is the skipped diene, but formation of a more stable cyclopentene is also possible. Understanding the underlying processes allowed for the development of divergent methodologies to selectively and controlledly obtain cyclopentene or skipped diene from vinylcyclopropane.