Synthesis, molecular structure, conformational analysis, and chemical properties of silicon-containing derivatives of quinolizidine

J Org Chem. 2012 Mar 2;77(5):2382-8. doi: 10.1021/jo202658n. Epub 2012 Feb 22.

Abstract

A silicon analog of quinolizidine 3,3,7,7-tetramethylhexahydro-1H-[1,4,2]oxazasilino[4,5-d][1,4,2]oxazasilin-9a-yl)methanol 3 was synthesized. X-ray diffraction analysis confirmed the trans configuration and low temperature NMR spectroscopy both the flexibility (barrier of interconversion 5.8 kcal mol(-1)) and the conformational equilibrium (chair-chair and chair-twist conformers) of the compound. The relative stability of the different isomers/conformers of 3 was calculated also at the MP2/6-311G(d,p) level of theory. Intra- and intermolecular hydrogen bonding in 3 and the appropriate equilibrium between free and self-associated molecules was studied in solvents of different polarity. Both the N-methyl quaternary ammonium salt and the O-trimethylsilyl derivative of 3 could be obtained and their structure determined.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Crystallography, X-Ray
  • Models, Molecular
  • Molecular Structure
  • Quinolizidines / chemical synthesis*
  • Quinolizidines / chemistry
  • Silicon / chemistry*

Substances

  • Quinolizidines
  • Silicon