Nonstatistical Dynamic Effects in the Thermal C-2-C-6 Diels-Alder Cyclization of Enyne-Allenes

SAMANTA D., Cinar M. E., DAS K., Schmittel M.

JOURNAL OF ORGANIC CHEMISTRY, cilt.78, sa.4, ss.1451-1462, 2013 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 78 Sayı: 4
  • Basım Tarihi: 2013
  • Doi Numarası: 10.1021/jo302524a
  • Dergi Adı: JOURNAL OF ORGANIC CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.1451-1462
  • İstanbul Teknik Üniversitesi Adresli: Hayır

Özet

The Diels-Alder (DA) reaction channel of the thermal C-2-C-6 (Schmittel) cyclization of enyne-allenes is studied computationally and experimentally evaluating the influence of temperature on product ratios. Remote substituents at the alkyne terminus influence the mechanism of the C-2-C-6/DA cyclization steering it either to a stepwise or a concerted course. Temperature independent product ratios, selectivity of product formation, and computational results obtained at (U)BLYP/6-31G(d) level unveil a mechanism that is strongly controlled by nonstatistical dynamics.