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, vol.80, no.16, pp.8175-8182, 2015 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 80 Issue: 16
  • Publication Date: 2015
  • Doi Number: 10.1021/acs.joc.5b01256
  • Journal Name: JOURNAL OF ORGANIC CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.8175-8182
  • Istanbul Technical University Affiliated: No

Abstract

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.