Mechanistic Information from Nonstationary Points


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

ORGANIC LETTERS, cilt.18, ss.84-87, 2016 (SCI İndekslerine Giren Dergi) identifier identifier

  • Cilt numarası: 18 Konu: 1
  • Basım Tarihi: 2016
  • Doi Numarası: 10.1021/acs.orglett.5b03310
  • Dergi Adı: ORGANIC LETTERS
  • Sayfa Sayıları: ss.84-87

Özet

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.