CAREER: Novel diastereoselective bond forming reactions via siliconate intermediates

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While in situ siliconate formation followed by hydride reduction of an oxocarbenium cation is a synthetically very valuable tool, expansion of this initial observation to include carbon based transfers are highly desirable to the synthetic community. Thus, the possibility of siliconate formation, carbon based nucleophilic shift to an oxocarbenium cation affording new diastereoselective carbon-carbon bonds, and concomitant silylation of the initial hydroxyl 'directing' group is a tremendous goal that this award addresses with respect to cyclic and acyclic stereocontrol. This project will further investigate the inclusion of carbon based nucleophiles which would greatly expand the reaction sequence beyond that of a hydride reduction of the oxocarbenium cation. This type of carbon group transfer should allow for the formation of quaternary or tertiary carbons dependent of the oxocarbenium substitution pattern and will make a tremendous impact on stereocontrolled carbon-carbon bond formation. In addition, the education portion of this CAREER award will provide a 'real world' research experience for highly motivated, underrepresented minority high school students from rural Alabama. This award will bring these young adults into the laboratory for their first encounter with scientific research. This exposure will help to foster and promote interests in future careers within the physical sciences. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Michael P. Jennings of the Department of Chemistry at The University of Alabama, Tuscaloosa. Professor Jennings' research efforts revolve around the development and further fundamental understanding of oxocarbenium cation reductions within the greater context of natural product synthesis. Successful development of the methodology will have an impact on synthesis in the pharmaceutical and agricultural industries.