Mechanistic Information from Nonstationary Points

RANA A., Cinar M. E. , SAMANTA D., Schmittel M.

ORGANIC LETTERS, vol.18, no.1, pp.84-87, 2016 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 18 Issue: 1
  • Publication Date: 2016
  • Doi Number: 10.1021/acs.orglett.5b03310
  • Title of Journal : ORGANIC LETTERS
  • Page Numbers: pp.84-87


The thermal cyclization of enyne-carbodiimides substituted at both the alkyne and carbodiimide terminus showed two curved Hammett correlations (log k/k(0) against sigma(P)) that were fully reproduced by DFT (density functional theory) computational results. The latter suggest a concerted mechanism, but the transition state (TS) analysis failed to reveal any mechanistic insight about the reason for a curved Hammett correlation. Instead a preTS inspection, i.e., examination of the electronic and steric details on route between reactant and TS, furnished a detailed picture of the mechanism.