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A forbidden rearrangement.

Martin Leivers1, Iris Tam, Kevin Groves

  • 1Department of Chemistry, Columbia University, New York, New York 10027, USA.

Organic Letters
|September 12, 2003
PubMed
Summary

Barrelene derivatives undergo fragmentation to yield benzene and cyanocyclopropenes. The barrelene anion rearranges via a formally forbidden cyclopropyl ring cleavage, forming an allyl anion.

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Area of Science:

  • Organic Chemistry
  • Reaction Mechanisms
  • Physical Organic Chemistry

Background:

  • Barrelene derivatives are strained polycyclic hydrocarbons.
  • Understanding the fragmentation and rearrangement pathways of strained molecules is crucial in organic chemistry.

Purpose of the Study:

  • To investigate the fragmentation products of a barrelene derivative.
  • To elucidate the mechanism of the barrelene anion's thermal rearrangement.
  • To rationalize a formally Woodward-Hoffmann-forbidden reaction.

Main Methods:

  • Chemical reaction analysis of barrelene derivatives.
  • Spectroscopic characterization of reaction products.
  • Theoretical analysis of reaction pathways.

Main Results:

  • Barrelene derivatives fragment to benzene and 1,2,3-tricyanocyclopropene.
  • The barrelene anion fragments to benzene and the 1,2,3-tricyanocyclopropenyl anion.
  • The major thermal product of the barrelene anion is a rearranged allyl anion, resulting from disrotatory cleavage of the cyclopropyl ring.

Conclusions:

  • The thermal rearrangement of the barrelene anion proceeds through a cyclopropyl ring cleavage that is formally forbidden by Woodward-Hoffmann rules.
  • Several mechanistic proposals are presented to explain this unexpected rearrangement pathway.

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