Theoretical study of the substituent effect of hydroxy group on tandem Cope rearrangement and [2 + 2] cycloaddition in cis-1,2-diethynylcyclopropane and its mono-hetero analogues

  • Manjinder Kour
  • Nivedita Sharma
  • Raj K. BansalEmail author
Original Research


The tandem Cope rearrangement and [2 + 2] cycloaddition of cis-1,2-diethynyl-1,2-dihydroxycyclopropane and its mono-hetero analogues have been investigated at the B3LYP/6-31+G* level. The presence of the hydroxy group lowers the activation enthalpies for the Cope rearrangement, whereas activation enthalpies for the [2 + 2] cycloaddition are raised as compared to those for their non-hydroxy derivatives. The NBO analysis indicates that in the transition structure involved in the Cope rearrangement, lone pairs of the oxygen atoms of the hydroxy groups are transferred into the σ* C–C bond undergoing migration, as a result of which it is weakened. On the other hand, the lone pairs of the oxygen atoms interact with the π* C=C orbitals of the bis-allenic systems in the intermediate thereby stabilizing it and, thus, suppressing its driving ability for the [2 + 2] cycloaddition. In the products so formed, 6π electrons are delocalized conferring stability on them, which is further augmented by extended conjugation with the hydroxy groups. Due to high stability of these products, activation barrier for the change of enol into ketone is very high.


cis-1,2-Diethynyl-1,2-dihydroxycyclopropane Cope rearrangement [2 + 2] Cycloaddition Effect of hydroxy group DFT studies 


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Conflict of interest

The authors declare that they have no conflict of interest.

Human and animal studies

This article does not contain any studies with human participants or animals performed by any of the authors.

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All authors have read and approved to submit it to your journal. This paper has not been submitted elsewhere for consideration of publication.

Supplementary material

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Authors and Affiliations

  1. 1.School of Applied SciencesSuresh Gyan Vihar UniversityJaipurIndia
  2. 2.Department of ChemistryThe IIS UniversityJaipurIndia

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