Asymmetric photochemical reaction of 5-methylbicyclo[1.1.1]-pentanyl ketone

Xiao Lin Wang*, Ke Zhang

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)

Abstract

The density functional theory(DFT) calculations were performed to investigate a typical Norrish/Yang type II photoreaction of 5-methylbicyclo[1.1.1]-pentanyl ketone. The results reveal the essential correlation between structures on the one hand and energies, on the other hand, of the reactants, transition states and products based on both singlet ground(S 0) and triplet excited(T 1) potential energy surfaces. The feasible mechanism indicates that an intramolecular Norrish/Yang cyclization reaction takes place via H-abstraction to obtain the sole chiral cyclobutanol photoproduct. The located crossing point plays an important role in the cyclization process, which permits intersystem crossing(ISC) from T 1 to S 0 state. The rate-determining step may be to experience ISC between two different potential energy surfaces, requiring sufficient time for electron spin reversion, i.e., spin multiplicity alteration. These conclusions are further confirmed by the second-order Møller-Plesset perturbation theory(MP2) calculations.

Original languageEnglish
Pages (from-to)703-706
Number of pages4
JournalChemical Research in Chinese Universities
Volume28
Issue number4
Publication statusPublished - Jul 2012

Keywords

  • Density functional theory(DFT)
  • Intersystem crossing
  • Norrish/Yang type II photoreaction
  • Reaction mechanism
  • Transition state

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Wang, X. L., & Zhang, K. (2012). Asymmetric photochemical reaction of 5-methylbicyclo[1.1.1]-pentanyl ketone. Chemical Research in Chinese Universities, 28(4), 703-706.