The Chemical Catalysis Program of the Chemistry Division of the National Science Foundation will support the research program of Professor Wenbin Lin of the University of North Carolina at Chapel Hill. Dr. Lin and his students are exploring the synthesis of enantioselective catalysts using strategies to incorporate active homogeneous catalysts into metal-organic framework materials. These "heterogenized" homogeneous catalysts are characterized for activity and selectivity, and information about the catalyst structure obtained from dye absorption/spectrometry and X-ray diffraction are used to design improved catalytic materials. New methodology, specifically the use of dye sensitized optical probes to determine pore size, and new synthetic approaches, which include functional framework members in the MOF synthetic routes, will result from this work. In addition, active enanatioselective catalyst materials will be produced. These catalytic materials will be useful for the synthesis of fine chemicals, medicinal chemistry intermediates, and for the design of stereospecific process routes for pharmaceuticals. High school students will work alongside undergraduate and graduate students in this broadly multidisciplinary research program.
During the funding period, we have developed a number of chiral metal-organic frameworks (MOFs) as efficient heterogeneous asymmetric catalysts for important organic transformations. We have prepared MOF-based heterogeneous asymmetric catalysts via postsynthetic modifications (PSMs) of isoreticular porous chiral MOFs and direct incorporation of catalytically competent struts. We successfully dlineated open channel size/catalytic performance relationships, developed an understanding on copperative actions, and shown MOF-based tandem reactions. We also demonstrated that MOFs can lead to highly active catalysts based on earth abundant metals. Our research efforts led to fundamentally new bottom-up approaches toward efficient heterogeneous asymmetric catalysts which can be readily recycled and re-used. They can also prevent leaching of often toxic metals into the organic products. Our efforts have led to innovative MOF-based chirotechnology that has the ability to promote health and safety and to ensure environmental stewardship. Lastly, this project signifacntly contributed to the mission of integrating research and eductaioon. A number of graduate students, postdoctoral fellows, undergrdauate students, and high school students have participated in the research activities. Due to the interdisciplinary nature of the project, these students have been trained with the skills that are crucial to their future careers. This project thus provided an excellent opportunity for the PI to engage in research and education.
