Issue 43, 2022

Computational investigation of cycloadditions between cyclopentadiene and tropone-3,4-dimethylester

Abstract

Thermally promoted cycloaddition reactions of tropone-3,4-dimethylester and cyclopentadiene have been investigated using density functional theory calculations at the M06-2X level and the CBS-QB3 method. The reaction shares several characteristics with previously investigated cycloadditions involving unsubstituted tropone and cyclopentadiene, however substitution of the tropone component with methyl esters results in lower transition state free energy barriers, greater thermodynamic driving forces, and a significant increase in the number of possible pericyclic reaction pathways. Eighteen different [4 + 2], [6 + 4], or [8 + 2] cycloaddition products are possible and many of the initially formed cycloadducts can be interconverted through Cope or Claisen rearrangements. Of the many possible cycloaddition products only two are predicted to form: the exo-[6 + 4] product and one [4 + 2] product where the substituted tropone appears to be the diene. The two computationally predicted products are the same as the two that are observed experimentally, however computations indicate that both products result from ambimodal processes rather than single-step (monomodal) cycloaddition pathways.

Graphical abstract: Computational investigation of cycloadditions between cyclopentadiene and tropone-3,4-dimethylester

Supplementary files

Article information

Article type
Paper
Submitted
05 Sep 2022
Accepted
10 Oct 2022
First published
11 Oct 2022

Org. Biomol. Chem., 2022,20, 8443-8453

Computational investigation of cycloadditions between cyclopentadiene and tropone-3,4-dimethylester

M. L. Milrod and B. H. Northrop, Org. Biomol. Chem., 2022, 20, 8443 DOI: 10.1039/D2OB01623K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements