Unexpected regioselectivity observed in the bromination and epoxidation reactions of p-benzoquinone-fused norbornadiene: An experimental and computational study


Essiz S., Dalkilic E., ÖZDEMİR SARI Ö. B., DAŞTAN A., Balci M.

Tetrahedron, cilt.73, sa.12, ss.1640-1649, 2017 (SCI-Expanded) identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 73 Sayı: 12
  • Basım Tarihi: 2017
  • Doi Numarası: 10.1016/j.tet.2017.02.017
  • Dergi Adı: Tetrahedron
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.1640-1649
  • Anahtar Kelimeler: 1,4-Benzoquinone, Bromination, Electrophilic addition, Epoxidation, Norbornadiene
  • Hakkari Üniversitesi Adresli: Evet

Özet

The bromination reaction of p-benzoquinone-fused norbornadiene was studied at various temperatures (−78, −50, 0, 25, and 77 °C). At room temperature, the double bonds of the p-benzoquinone units were mainly brominated. The double bond of the norbornene unit also underwent a bromination reaction in a yield of only 2%. However, the reaction at −78 °C resulted in the formation of products derived from the attack of bromine on the norbornene double bond with higher charge density. In contrast to the bromination reaction, the epoxidation reaction of the same compound with m-chloroperbenzoic acid and dimethyldioxirane exclusively resulted in the formation of products derived from the addition to the double bond of norbornadiene. The regioselectivity observed was investigated and the results were supported by theoretical calculations.