Enantioselective Installation of Quaternary Centers in Cyclic Oxonitriles

Gunes Y., Arcelik N., ŞAHİN E., Fleming F. F., Altundas R.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, cilt.2015, sa.30, ss.6679-6686, 2015 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 2015 Sayı: 30
  • Basım Tarihi: 2015
  • Doi Numarası: 10.1002/ejoc.201500895
  • Dergi Adı: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.6679-6686
  • Anahtar Kelimeler: Synthetic methods, Asymmetric synthesis, Rearrangement, Sigmatropic rearrangement, Alkylation, STEREOSELECTIVE CONSTRUCTION, ASYMMETRIC-SYNTHESIS, REARRANGEMENTS
  • Atatürk Üniversitesi Adresli: Evet

Özet

Quaternary centers are rapidly and selectively installed in a series of seven-membered and bridged cyclic oxonitriles through conjugate addition of an alkoxide to chloroalkenenitriles, followed by a Claisen rearrangement. Using this strategy, the stereogenic information of the carbinol in secondary allylic alcohols is transferred to the newly generated quaternary center. Experimentally, the sequence rapidly gives alkyl cyanocycloheptanones and bicycloalkanonecarbonitriles in good yield and with high selectivity, in a single synthetic operation.