Radical mediated deoxygenation of inositol benzylidene acetals: conformational analysis, DFT calculations, and mechanism

Carbohydr Res. 2012 Apr 1:351:26-34. doi: 10.1016/j.carres.2012.01.001. Epub 2012 Jan 13.

Abstract

Xanthates of 1,3-benzylidene acetal derivatives of myo- and neo-inositols undergo dideoxygenation under Barton-McCombie conditions, as a result of intramolecular abstraction of the benzylidene acetal hydrogen and subsequent cleavage of the acetal ring. Scrutiny of structure of these bicyclic inositol derivatives shows that although the conformation of the two rings can vary depending on the configuration of the inositol ring and the phase in which the molecules are present, both the xanthates lead to the formation of the same dideoxyinositol. DFT calculations on these molecular systems suggest that neo-inositol derivatives undergo conformational change prior to radical formation while myo-inositol derivatives undergo conformational change subsequent to radical formation, during the deoxygenation reaction. A low barrier for intramolecular hydrogen transfer supports the extreme facility of this deoxygenation reaction.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetals / chemistry*
  • Benzylidene Compounds / chemistry*
  • Free Radicals / chemistry
  • Inositol / chemistry*
  • Models, Molecular
  • Molecular Conformation*
  • Oxygen / chemistry*
  • Quantum Theory*

Substances

  • Acetals
  • Benzylidene Compounds
  • Free Radicals
  • Inositol
  • Oxygen