Fluoro-Ene Reaction Versus [2+2] Cycloaddition in the Thermal C-2-C-6 Cyclization of Enyne-Allenes: An Experimental and Theoretical Investigation

Cinar M. E., VAVILALA C., JAQUET R., BATS J. W., Schmittel M.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, sa.24, ss.5166-5177, 2014 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Basım Tarihi: 2014
  • Doi Numarası: 10.1002/ejoc.201402438
  • Dergi Adı: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.5166-5177
  • İstanbul Teknik Üniversitesi Adresli: Hayır

Özet

A series of fluoroalkyl-substituted enyne-allenes have been synthesized by a new route with the aim of elucidating the possibility of a fluoro-ene reaction via an intermediate fulvenyl diradical generated in the thermal C-2-C-6 (Schmittel) cyclization reaction. As a result of the strong C-F bond, fluorine atom transfer was not observed. Instead, 1H-cyclobuta-[a]indenes were formed in good yields despite the high strain energy. DFT calculations at the B3LYP level of theory indicated that although the fluoro-ene reaction is the most exothermic reaction available, cyclobutene formation is kinetically favored over the [1,5]-fluorine shift by 5-15 kcalmol(-1) in various model compounds.