This award is funded under the American Recovery and Reinvestment Act of 2009 (Public Law 111-5). This project will continue work on the further development of Ir(I)-catalyzed enantioselective decarboxylative allylic amidation reaction and the corresponding intermolecular allylic amidation reaction, with particular emphasis on their synthetic utility and potential. Particularly interesting to study is enantioselective (decarboxylative) allylic amidation of allylic diene systems, which can generate a broad range of optically enriched 'orthogonally' protected 1,2-/1,3-/1,4-diamines/aminoalcohols, for which no general synthetic method exists. Also demonstrated is that the developed (decarboxylative) enantioselective allylic amidation reactions, in conjunction with enantioselective (decarboxylative) allylic etherification, stereoselective intramolecular amidomercuration, and olefin metathesis reactions, can provide extremely general and efficient strategies for the asymmetric synthesis of the core structural motifs of many biologically significant and synthetically challenging compounds such as (polyhydroxylated) pyrrolidine and piperidine rings, (polyhydroxylated) indolizidine and pyrrolizidine rings, and aza-C-glycosides.
With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Hyunsoo Han of the Department of Chemistry at the University of Texas at San Antonio. Professor Han's research efforts revolve around the development of enantioselective (decarboxylative) allylic amidation and etherification reactions for the formation of C-N/O bonds. Considering the ubiquitous presence of C-N/O bonds in almost all biologically significant organic compounds, successful development of this project will have an impact on synthesis in the pharmaceutical, biomedical, and agricultural industries.
