Jump to main content
Jump to site search

Issue 9, 2019
Previous Article Next Article

The chiral photocycloaddition of a cyclohexenone derivative with a chiral alkene. A DFT study

Author affiliations

Abstract

The photochemical reaction of 3-carboxymethylcyclohexenone with a cyclohexene bearing a chiral auxiliary group has been examined in a DFT study. GIAO simulation of the NMR spectra (DFT/B3LYP/6-311G++(d,2p) level of theory) is not in agreement with the synantisyn product described in the literature for this reaction but is in agreement with the formation of a syncissyn dimer. The analysis of the frontier orbitals involved in this reaction shows that the main interaction is that between the HOMO of the alkene and the LSOMO of the carbonyl compound in its first excited triplet state. The atomic coefficients do not allow a frontier orbital control of the regiochemistry of the reaction. The study of the possible biradical intermediates and the energies of the transition states involved agree with the formation of a syncissyn biradical intermediate. The coupling of the radical carbon atoms in this biradical intermediate allows the obtainment of a more stable dimer. Furthermore, the coupling reaction occurs via a conrotatory process that is able to give only one of the possible syncissyn dimers.

Graphical abstract: The chiral photocycloaddition of a cyclohexenone derivative with a chiral alkene. A DFT study

Back to tab navigation

Supplementary files

Publication details

The article was received on 15 Nov 2018, accepted on 25 Feb 2019 and first published on 26 Feb 2019


Article type: Paper
DOI: 10.1039/C8PP00521D
Photochem. Photobiol. Sci., 2019,18, 2191-2198

  •   Request permissions

    The chiral photocycloaddition of a cyclohexenone derivative with a chiral alkene. A DFT study

    M. D'Auria, Photochem. Photobiol. Sci., 2019, 18, 2191
    DOI: 10.1039/C8PP00521D

Search articles by author

Spotlight

Advertisements