One-Pot Domino Aldol Reaction of Indium Enolates Affording 6-Deoxy-alpha-D,L-altropyranose Derivatives: Synthesis, Mechanism, and Computational Results

Cinar M. E., Schmittel M.

JOURNAL OF ORGANIC CHEMISTRY, cilt.80, sa.16, ss.8175-8182, 2015 (SCI-Expanded) identifier identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 80 Sayı: 16
  • Basım Tarihi: 2015
  • Doi Numarası: 10.1021/acs.joc.5b01256
  • Dergi Adı: JOURNAL OF ORGANIC CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.8175-8182
  • İstanbul Teknik Üniversitesi Adresli: Hayır

Özet

The domino-aldol-aldol-hemiacetal-reaction cascade of indium and other group 13 metal enolates furnished 6-deoxy-alpha-D,L-altropyranose derivatives in up to 99% yield under thermodynamic control. At lower temperature and thus under kinetic control, the reaction proceeded in a much less diastereoselective manner. The changeover from kinetic to thermodynamic control operating in this multistep domino-aldol-aldol-hemiacetal protocol was used for probing the efficiency of DFT computations. Calculations at the B3LYP/6-31G(d)/LANL2DZ level provided a mechanistic picture in full agreement with the experimental outcome.