Stereoselective Oxidation of an Eleven-Membered Heterocycle

Abstract

Oxidation of macrocyclic phosphine oxide-dithioether 1 produces only the dl form of disulfoxide 2. This selectivity can be rationalized by comparing the crystal structures of starting material and product, and on the basis of VT NMR data, which suggest that the starting macrocycle is conformationally constrained in solution. Molecules containing multiple sulfoxide and/or phosphine oxide groups are of interest as potential hosts for cations and for neutral guests bearing multiple hydrogen bond donors. As part of our exploration of such systems, we have prepared macrocycle 1 and oxidized it to disulfoxide 2. We report here that this oxidation is selective, providing only the dl product; neither of the meso stereoisomers was detected. Structural data for starting material and product suggest that this selectivity results from the conformational preference of eleven-membered ring of 1.

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Document Details

Document Type
Technical Report
Publication Date
Jan 01, 1992
Accession Number
ADA252091

Entities

People

  • John M. Desper
  • Paul B. Savage
  • Samuel H. Gellman

Tags

Communities of Interest

  • Biomedical

DTIC Thesaurus Topics

  • Abstracts
  • Chemistry
  • Chromatographic Analysis
  • Crystal Structure
  • Crystals
  • Hydrogen
  • Low Temperature
  • Military Research
  • Organic Chemistry
  • Organophosphorus Compounds
  • Oxidation
  • Oxides
  • Phosphine
  • Phosphine Oxides
  • United States
  • Universities
  • Wisconsin

Fields of Study

  • Chemistry

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  • Organic Chemistry