This project represents a continuation of Professor Krische's efforts toward the development of phosphine catalyzed C-C and C-N bond forming processes. Prior to studies from Professor Krische's group, Morita-Baylis-Hillman type couplings were largely restricted to the use of aldehydes and aldimines as electrophilic partners. The Krische group has expanded the range of electrophilic partners applicable to MBH-type coupling to encompass enones, allylic acetates and arenes. In the proposed funding period, enantioselective variants of these transformations will be devised and other phosphine catalyzed processes will be developed.
With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Michael J. Krische at the Department of Chemistry and Biochemistry at the University of Texas at Austin. Professor Krische's research program focuses on catalytic reaction development, in particular on byproduct-free processes for C-C and C-N bond formation. The successful development of the proposed methodologies will have a large positive impact on synthetic organic chemistry in the pharmaceutical and agrochemical industries.
Our collective studies on phosphine organocatalysis (made prior to and during this grant) have solidified this area as a distinct field of research. Our initial publication in this area (JACS 2002, 2402) has been cited over 150 times, and another early contribution of ours to this field (Org. Lett. 2004, 1337) has been cited over 100 times. One major accomplishment achieved during the 3-year funding period involves application of a phosphine catalyzed cycloallylation process developed in our laboratory in a concise stereoselective syntheses of (±)-quinine and (±)-7-hydroxyquinine (J. Org. Chem. 2008, 73, 9379). Quinine is a treatment for malaria, which is the number one killer of human beings. Using a catalytic reaction developed under the aegis of NSF support, we have developed the most concise approach to quinine, to date (J. Org. Chem. 2008, 73, 9379). In the course of the funding period, two graduate student participants (Pete Webber and Regan Jones) received PhD degrees and are now employed at NALCO. Olivia Webber, an African American undergraduate who performed research under my mentorship, received a BS degree and is now employed in the chemical industry. Justin Romaire, an undergraduate from Louisiana, was mentored in my laboratory for a summer in connection with the NSF-REU program. Additionally, I am serving as thesis advisor to two male African American graduate students, Chris Grant and Brannon Sam, who are now doctoral candidates in the graduate program at UT Austin. Finally, my laboratory has launched the 'Center for Green Chemistry and Catalysis' - to my knowledge, the first Green Chemistry center at a university in Texas. The research funded under the aegis of this NSF grant fall within the purview of this center, the mission of which is to promote and raise awareness of Green Chemistry in Texas.
