SGER: Investigation of Electron-Deficient Oxygen Sources and Application to Unprecedented Carbon-to-Oxygen Rearrangements

University Of Vermont & State Agricultural College, Burlington VT

Investigators

Abstract

The goal of this proposal is to develop an unprecedented carbon-to-oxygen rearrangement that would convert alcohols into oxygen-containing heterocycles. Currently, peroxides undergo the only known carbon-to-oxygen migration. These known peroxide-based rearrangements are of limited utility because the peroxide starting materials pose explosion hazards and are not easily prepared or handled. Sulfur-oxygen linkages will be tuned to provide the same rearrangement reactivity profile as peroxides. These studies will focus on preparing a series of alkoxysulfonium ions and sulfenic esters with differing electronic and steric properties to evaluate the criteria necessary to induce such a rearrangement. These transformations may provide oxocarbenium ion intermediates, opening the possibility of performing tandem reactions to produce complex oxygen-containing polycyclic products from simple alcohol starting materials. With the support of this Small Grants for Exploratory Research award from the Organic and Macromolecular Chemistry Program, Professor Matthias Brewer, of the Department of Chemistry at the University of Vermont, is studying new methods to prepare oxygen-containing heterocycles. Oxygen-containing heterocycles are present in biologically active compounds used therapeutically as antibiotics, cardiovascular agents, neurological modulators, antiasthmatic agents, antiinflammatory agents, antidiabetic agents and vaccines. These compounds are often synthetically challenging and difficult to prepare, limiting their use in biomedical studies. Professor Brewer's methodology will greatly facilitate the preparation of these compounds, which in turn will facilitate their use in biomedical research and could lead to new and improved medicinal agents.