Pyramidalized double bonds containing endoperoxide linkages: Photooxygenation of dimethyl cis-3,8-dihydroheptalene-3,8-dicarboxylate
JOURNAL OF ORGANIC CHEMISTRY, cilt.64, sa.18, ss.6670-6676, 1999 (SCI-Expanded, Scopus)
- Yayın Türü: Makale / Tam Makale
- Cilt numarası: 64 Sayı: 18
- Basım Tarihi: 1999
- Doi Numarası: 10.1021/jo990393o
- Dergi Adı: JOURNAL OF ORGANIC CHEMISTRY
- Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
- Sayfa Sayıları: ss.6670-6676
- Açık Arşiv Koleksiyonu: AVESİS Açık Erişim Koleksiyonu
- Orta Doğu Teknik Üniversitesi Adresli: Hayır
Özet
Diels-Alder cyclo;addition utilizing singlet oxygen as the dienophile with dimethyl cis-3,8-dihydraheptalene-3,8-dicarboxylate (5) has been investigated, and monoaddition product 7 has been isolated. The addition of a second singlet oxygen to the cycloheptatriene unit in 7 gave syn-bis(norcaradiene) bis(endoperoxide) 4. H-1 NMR spectral studies and theoretical calculations indicate the increased pyramidalization in syn-4 compared with carbon analogue. The increased pyramidalization results from hyperconjugation between the central pi-bond and the four adjacent C-O bonds and by rehybridization at C3, C4, C5, and C6. Furthermore, the increased reactivity for syn-4, which is probably arising from further folding of the central double band, is also in agreement with theoretical calculations.