Heterocycle Synthesis Through Reversible Allylic Alcohol Transposition and Stereoselective Capture

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In this project funded by the Synthesis Program of the Chemistry Division, Prof. Paul Floreancig at the University of Pittsburgh develops new chemical reactions in which reversibility is coupled with a secondary step to increase molecular complexity and generate stereocenters. The approach is to expose allylic alcohols that contain an electrophilic group to rhenium oxide or other catalysts that effect non-stereoselective transpositions. The transposition will proceed until an intramolecular reaction occurs in which stereochemical control will be dictated by thermodynamic, kinetic, or catalyst control. A number of elements will be incorporated into the reaction substrates to demonstrate that reaction outcomes can be manipulated rationally through applications of basic principles and molecular modeling. The target structures have been selected due to their relevance to the synthesis of natural products. The coupling of stereocontrol with ring formation that will be developed in this work can significantly reduce the effort that is required for complex molecule synthesis. This will benefit the fields of medicinal chemistry and materials science. The mild conditions that are used for these reactions will make the processes attractive for chemical manufacturing applications. The broader impacts of this work lie in the use of these processes as a tool for highlighting the manner in which thermodynamics and kinetics can be manipulated for complex reaction design, and in the use of travel funds to present seminars at colleges that have a high enrollment of underrepresented minority students. In addition, this project provides research training to graduate students and contributes to workforce development.