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Divergent Rearrangements of Vinylcyclopropane into Skipped Diene and Cyclopentene: Mechanism, Scope, and Limitations
Author(s) -
Delbrassinne Arnaud,
Richald Maximilien,
Janssens Julien,
Robiette Raphaël
Publication year - 2021
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202100430
Subject(s) - cyclopentene , cyclopropane , chemistry , diene , regioselectivity , ring (chemistry) , stereochemistry , organic chemistry , catalysis , natural rubber
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.