9408980 Gladysz Univ. of Utah Dr. John Gladysz, Chemistry Department, University of Utah, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program to develop the organometallic chemistry of Re to provide new methods of asymmetric synthesis and routes to long , linear chains containing only carbon atoms. In the first of these projects a highly diastereoselective 2,3 sigmatropic rearrangement of chiral rhenium sulfur-ylide compounds will be used to thio-derivatives in high enantiomeric purity. In the second portion, acetylenic fragments, in which one end is attached to an organorhenium moiety, will be oxidatively coupled to form linear carbon chains which are 4, 8, 9, and 16 atoms long. The mechanisms of the various reactions and delocalization of unpaired electrons within the carbon chains will be studied. Many molecules exist in two mirror image forms which are not the same (similar to right and left handed gloves). Many biologically important molecules are of this type and often the two mirror image form have very different properties. Consequently, the ability to selectively form a single form is of great importance to, e.g., the pharmaceutical and agrichemical industries. In this project a new method of accomplishing some highly selective syntheses of important sulfur containing compounds will be developed. In a second part of the study long chains of composed only of carbon atoms will be prepared. These are of interest because of they may form the basis of electrically conducting, wire-like molecules.
