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Selective, Catalytic Functionalization of
C-H Bonds with Small and Large Catalysts


The selective introduction of functional groups into complex molecules at the positions of C-H bonds has been a longstanding challenge in catalysis. Our group has developed practical methods for the catalytic functionalization of C-H bonds with main group reagents, such as boranes and silanes, to create a comprehensive strategy to use one C-H bond functionalization process to form a range of products. 

This catalysis inspired us to combine the reactions of C-H bonds catalyzed by small transition-metal complexes with the selectivity and evolutionary potential of enzymes. To do so, we have created artificial heme enzymes in which the iron of the heme has been replaced with noble metals to create catalysts for reactions that have not been catalyzed by natural or mutant heme enzymes.

This lecture will present recent directions of research in our group toward discovering selective reactions of C-H bonds catalyzed by both transition metal complexes and
artificial metalloenzymes. The design and selection, as well as the intimate mechanism, of catalysts and catalytic reactions for these selective functionalization processes
will be presented.

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Photo of Professor John Hartwig

Professor John F. Hartwig
Department of Chemistry
University of California, Berkeley

John F. Hartwig is the Henry Rapoport Chair in Organic Chemistry at UC Berkeley. He was born in Elmhurst, Ill., and studied at Princeton University (BA in Chemistry) and the University of California, Berkeley (PhD in Chemistry). After a postdoctoral appointment at MIT (1990–92), he joined the faculty of Yale University (1992–2006) as an assistant professor and ultimately the Irenée P. DuPont Professor of Chemistry. In 2006, he moved to the University of Illinois at Urbana Champaign, where he was the Kenneth L. Rinehart Professor (2006–2011), and in 2011, he returned to UC Berkeley, where he has spent the past eight years. His research spans the fields of inorganic, organometallic
and organic chemistry. His research group focuses on the discovery and understanding of new reactions of organic molecules catalyzed by transition metal complexes.

He is well known for contributions to widely practiced cross-coupling chemistry that forms arylamines, aryl ethers, aryl sulfides and α-aryl carbonyl compounds, and
for the discovery of practical C-H bond functionalization reactions.

He discovered an iridium catalyst that has become one of the most utilized for enantioselective allylic substitution, published the most active catalysts for the hydroamination of unactivated alkenes, and developed a reliable reagent for the trifluoromethylation of aryl halides. While developing these systems, 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.

He is the author of the widely used textbook, "Organotransition Metal Chemistry: From Bonding to Catalysis," which has been translated into foreign languages. He has published over 404 articles on these and other subjects, and has supervised the research of more than 175 PhD graduate students and postdoctoral researchers, in addition to numerous undergraduate researchers. His honors include the Wolf Prize in
Chemistry (2019), the Tetrahedron Prize for Creativity in Organic Chemistry (2018), the Centenary Prize from the Royal Society of Chemistry (2018) and the J. Willard Gibbs Medal Award (2015). He received a Cope Scholar Award, the H.C. Brown Award in Synthetic Methods and the ACS Award in Organometallic Chemistry from the
American Chemical Society. He was elected a Fellow of the Royal Society of Chemistry (2018) and is a member of both the American Academy of Arts and Sciences
(2015) and National Academy of Sciences (2012).

 



Professor John J. Eisch

John Joseph Eisch joined the Department of Chemistry at Binghamton University in 1972, as chair and professor of chemistry, with the mandate of fostering the national reputation of its graduate teaching and research. Over the next six years as chair, he guided the recruiting of six senior and junior faculty with this goal in mind, while expanding his own research in organometallic chemistry to a yearly group of eight to 12 graduate and postdoctoral students, with support from federal and industrial resources. In 1983, his composite achievements were recognized by his promotion to the SUNY-wide rank of distinguished professor of chemistry. Further recruiting, notably during the chair tenure of professors Eugene Stevens, Alistair Lees, Wayne Jones and currently, Eriks Rozners, expanded the scope of advanced research into areas of immediate importance, such as nano materials, homogeneous catalysis, analytical sensors, biological transformations and energy storage.

Eisch received the BS degree in chemistry, summa cum laude, from Marquette University in 1952; earned the PhD degree in 1956, with Henry Gilman, at Iowa State University; and served as Union Carbide Research Fellow with Karl Ziegler at the Max-Planck-Institut für Kohlenforschung, Mülheim, Germany (1956–57).  After junior professional appointments at St. Louis University and the University of Michigan, he became ordinary professor and department head at the Catholic University of America (1963–1972). He retired from his professorial career of 57 years in 2014, the latter 42 years of which were spent at Binghamton University.

The Eisch Group initially had concentrated on the preparation and organic synthetic uses of organometallic reagents of Li, Na, Mg, B and Al, but we were struck by the lack of definitive molecular mechanistic studies in previous work. In ensuing research encompassing reaction kinetics, trapping of any intermediates, IR, UV and X-ray crystallographic measurements, both heterolytic and homolytic C-M cleavages could be involved, as well as 4-centertrapesoidal transition states. Reviews are available in a) “Fifty Years of Ziegler- Natta Polymerization: From Serendipity to Science,” Organometallics, 2012, 31, 4917–4932 and b) Dalton Transactions, (DOI: 10:1039/c4dt010362) “Emergence of Electrophilic Alumination as the Counterpart of Established Nucleophilic Lithiation.” The original seven articles dealing with the reactions of RLi with the azomethyne groups have been recently published by the Eisch and the Rheingold Crystallographic Group in the European Journal of Organic Chemistry.

Over the years, the research involved the fruitful collaboration of more than 200 students as master’s, doctoral, postdoctoral or baccalaureate associates. The results have been reported in more than 410 scientific publications, in some 280 invited lectures worldwide, in the monograph “The Chemistry of Organometallic Compounds” (Macmillian, 1967) and in the edited series, “Organometallic Syntheses” (four volumes, J. J. Eisch and R. B. King, authors and editors). He has been an industrial consultant on organometallic chemistry and an expert witness in several patent litigations on Ziegler-Natta polymerization catalysis.

 One of the significant discoveries of our studies is that the reaction of organic carbanionic reagents is not a one-step nucleophilic C alpha attack (i) but a two-step electrontransfer and electron-coupling process (ii)(iii).

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Previous Lectureship Recipients

2012
Stephen L. Buchwald

MIT

“Palladium-Catalyzed CarbonNitrogen and Carbon-Carbon Bond-Forming Reactions: Progress, Applications and Mechanistic Studies”


2013
David W. C. MacMillan

Princeton University

“The Use of Photoredox Catalysis in New Organic Bond Forming Reactions”


2014
Brian M. Stoltz

California Institute of Technology

“Complex Natural Products as a Driving Force for Discovery in Organic Chemistry”


2015
Eric N. Jacobsen

Harvard University

“Anion-Binding Catalysis”


2016
Bob Crabtree

Yale University

“Organometallic Catalysis for Solar Fuels and Storage”

Phil S. Baran
The Scripps Research Institute

“Translational Chemistry”


2017
Stephen J. Lippard

MIT

“Understanding and Improving Platinum Anticancer Drugs”

Daniel A. Singleton
Texas A&M Uniersity

“Dynamic Effects and Energy Labeling in Free-Radical Reactions”


2018
Clifford P. Kubiak

University of California, San Diego

“If You Make a Solar Fuel From CO2, What Should It Be?”

Scott E. Denmark
University of Illinois at Urbana-Champaign

"Lewis-base Activation of Lewis Acids: An Evolving Paradigm for
Catalysis in Main Group Chemistry"

Last Updated: 4/10/19