Chemical Society Seminar: John Hartwig-Catalytic Functionalization of C-H bonds in Small and Large Molecules with Small and Large Catalysts

Abstract:

The selective introduction of functional groups at the positions of typically unreactive C-H bonds has been a longstanding challenge in catalysis. To this end, our group has developed practical methods for the catalytic functionalization of C-H bonds with main group reagents.^1-4 These studies have led us to a general strategy of installing a single transient functional group to form a range of products from one C-H bond functionalization reaction. This research has led us to seek next-generation catalysts for the functionalization of C-H in complex molecules, new classes of reactions for functionalization of these bonds, new strategies, such as the construction of artificial metalloenzymes to control the site at which such reactions occur,⁵ new ways for such enzymes and natural enzymes to work in concert to form unnatural products through artificial biosynthetic pathways,⁶ and new ways to deconstruct or change the properties of polyolefins by reactions initiated at C-H bonds. The design and selection, as well as the intimate mechanism, of catalysts and catalytic reactions for such functionalization processes will be presented.

Bio:

John Hartwig was born outside of Chicago, spent his childhood in upstate New York, and received his A.B. from Princeton University. He received his Ph.D. from U.C. Berkeley with Bob Bergman and Richard Andersen and conducted a postdoctoral fellowship at MIT with Stephen Lippard. In 1992 he began his independent career at Yale University and became the Irenée P. DuPont Professor in 2004. In 2006, he moved to the University of Illinois, where he was the Kenneth L. Rinehart Jr. Professor of Chemistry, and in 2011, he returned to U.C. Berkley as the Henry Rapoport Professor.

Professor Hartwig's research focuses on the discovery and understanding of new reactions for organic synthesis catalyzed by transition metal complexes. He is well known for contributions to widely practiced cross-coupling chemistry that form arylamines, aryl ethers, aryl sulfides, and a-aryl carbonyl compounds and for the discovery of practical C-H bond functionalization reactions, in addition to his work on the direct conversion of carbonyl compounds to alpha-aryl carbonyl derivatives, catalysts for the addition of amines alkenes, and highly selective catalysts for the regio and enantioselective amination of allylic carbonates. He has focused on the mechanism and fundamental organometallic chemistry that underpins them, including studies on reductive eliminations to form carbon-heteroatom bonds, oxidative addition of N-H bonds, and olefin insertions into amides and alkoxides. Since moving to Berkeley, he has also been studying catalysis with artificial metalloenzymes and artificial biosynthetic pathways, as well as conversions of biomass to chemicals and upcycling of polyolefins. He is the author of the textbook “Organotransition Metal Chemistry: From Bonding to Catalysis.” Outside the lab, he enjoys cooking, music, and activities outdoors.