Our group is focused on solving problems in selective catalysis. Currently, we are interested in developing small molecule catalysts capable of coordinating sequential and selective proton, electron, and H-atom transfer events within a discrete catalytic cycle. To this end, we are developing synthetic forms of a key component of the molecular machinery involved in photosynthesis to selectively remodel the connectivity of C-H bonds within molecules of interest. The immediate practical benefits of this work will be to provide chemists with tools to transform inexpensive feedstocks into valuable products containing stereocomplex C-H bonds, streamlining the synthesis of important chiral molecules. The broader aims of this work focus on using newly discovered reactions as a platform for studying fundamental mechanistic questions concerning the relationships between bond strengths, redox properties, protonation state and molecular recognition in catalysis. These studies may ultimately yield principles that will aid the development of new technologies and their associated applications in the synthesis of bioactive natural products, pharmaceuticals, and functional materials.
Selected Recent Publications
- Total Synthesis of Diazonamide A. Knowles, R. R.; Carpenter, J. E.; Blakey, S. B.; Kayano, A.; Mangion, I. K.; MacMillan D. W. C. Chemical Science 2011, 2, 308–311.
- Attractive Non-Covalent Interactions in Asymmetric Catalysis: Links Between Enzymes and Small-Molecule Catalysts. Knowles, R. R.; Jacobsen, E. N. Proc. Nat. Acad. Sci. USA 2010, 107, 20678–20685.
- Concerning the Mechanism of the FeCl3-Cataylzed a-Oxyamination of Aldehydes. Evidence for a Non-SOMO Activation Pathway. Van Humbeck, J. F.; Simonovich, S. P.; Knowles, R. R.; MacMillan D. W. C. J. Am. Chem. Soc. 2010, 132, 10012–10014.
- Enantioselective Thiourea-Catalyzed Cationic Polycyclizations. Knowles, R. R.; Lin, S.; Jacobsen, E. N. J. Am. Chem. Soc. 2010, 132, 5030–5032.