Robert Maleczka
Professor Office: 540 Chemistry
Phone: 517-355-9715 124 /
Websites: Research Group - Area
Awards & Honors
Genealogy/Graduates
Synthetic Organic Chemistry
(Research Description PDF - 1148 kb)Our group is interested in a) the total synthesis of biologically important natural products, b) the invention of new reactions and strategies in organic synthesis, and c) green chemistry.
Green Chemistry: Central to our research is the development of efficient and environmentally benign reactions and strategies. The Pharmaceutical Roundtable of the American Chemical Society's Green Chemistry Institute deemed cross-couplings that avoid haloaromatics as their top aspirational reaction. In collaboration with Professor Mitch Smith, we are inventing such reactions. Specifically, we are using catalytic C-H activation/borylation, often combined with subsequent chemical events, to generate pharmaceutically relevant building blocks for organic synthesis. We were honored when the U.S. Environmental Protection Agency recognized this chemistry with its 2008 Presidential Green Chemistry Challenge Award.
Another of our green chemistry ventures aims to minimizing the need for tin in various processes. For example, we were first to develop a Stille reaction that is catalytic in tin. We are now studying the kinetics and mechanism of this process so as to develop the next generation of this sequence.
Invention of New Reactions: The principles of green chemistry also motivate us to create new synthetic methods. Here we have been focusing on the employment of organosilanes as both reagents and substrates in chemical transformations ranging from Pd-mediated reductions, to enzymatic kinetic resolutions, to Wittig rearrangements.
Total Synthesis: The unifying thesis behind all of our methodological and mechanistic studies is that the chemistry to emerge from such studies should be applicable to real synthetic problems. We view target synthesis as the best proof of this concept. For example, we look to make monocillin I with reactions that only employ catalytic amounts of tin. Similarly, our route to autolytimycin involves the strategic application of a catalytic borylation/amidation/oxidation sequence developed as part of our green chemistry program.
Selected Publications
Iridium-Catalyzed Borylation of Thiophenes: Versatile, Synthetic Elaboration Founded on Selective C?H Functionalization, G. A. Chotana, V. A. Kallepalli, R. E. Maleczka, Jr., and M. R. Smith, III, Tetrahedron 2008, 64, 6103.Bismuth Pentafluoride, S.-H. Kim and R. E. Maleczka, Jr. in eEROS?Electronic Encyclopedia of Reagents for Organic Synthesis; Paquette, L. A.; Crich, D.; Fuchs, P. L.; Molander, G. A., Eds.; Wiley: New York (2007).
Ir-Catalyzed Functionalization of 2-Substituted Indoles at the 7-Position: Nitrogen-Directed Aromatic Borylation, S. Paul, G. A. Chotana, D. Holmes, R. C. Reichle, R. E. Maleczka, Jr., and M. R. Smith, III, J. Am. Chem. Soc. 2006, 128, 15552.
Pd-Catalyzed Silane/Siloxane Reductions in the One- Pot Conversion of Nitro Compounds to Their Amines, Hydroxylamines, Amides, Sulfonamides, and Carbamates, Rahaim, Jr. and R. E. Maleczka, Jr., Synthesis 2006, 3316.
a-Substituted Acylsilanes via a Highly Selective [1,4]- Wittig Rearrangement of a-Benzyloxyallylsilane, E. N. Onyeozili and R. E. Maleczka, Jr., Chem Commun. 2006, 2466.
Pd(0)-Catalyzed PMHS Reductions of Aromatic Acid Chlorides to Aldehydes, K. Lee and R. E. Maleczka, Jr., Org. Lett. 2006, 8, 1887.
