15th Biannual: John Eisch Lectureship In
Organic Chemistry
Friday March 17, 2023
4 P.M.
Smart Energy Building, Fountain Room
Pericyclic Reactions: Theory, Mechanisms, Dynamics and Role in Biology
Pericyclic reactions were defined by Woodward and Hoffmann in the 1960s. Pericyclic
reactions are concerted processes involving a cyclic reorganization of bonding. Computational
studies will be described focusing on four recent discoveries:
1) defining mechanisms of these reactions in terms of dynamics of bonding changes;
2) finding ambimodal polypericyclic transition states that give more than one product;
3) explaining orbital symmetry forbidden reactions that nevertheless occur readily;
and
4) identifying the role of pericyclic reactions in biosynthesis, catalyzed by a class
of enzymes that we have named pericyclases.
Professor Kendall N. Houk
Department of Chemistry and Biochemistry
University of California, Los Angeles
- Information about Professor Kendall N. Houk
K.N. Houk received his AB, MS and PhD degrees at Harvard, working with R.B. Woodward on experimental tests of orbital symmetry selection rules. In 1968, he joined the faculty at Louisiana State University, moved to the University of Pittsburgh in 1980, and to UCLA in 1986. From 1988–1990, he was director of the Chemistry Division of the National Science Foundation and from 1991–94, he served as chairman of the UCLA Department of Chemistry and Biochemistry. In 2009, he became the Saul Winstein chair in organic chemistry.
Recognized for his work, Professor Houk has received numerous awards including the von Humboldt Foundation U.S. Senior Scientist Award (1981), an Arthur C. Cope Scholar Award from the ACS (1988), the ACS James Flack Norris Award in Physical Organic Chemistry (1991), the Schrödinger Medal of the World Association of Theoretical and Computational Chemists (WATOC, 1998), the ACS Award for Computers in Chemical and Pharmaceutical Sciences (2003), the Arthur C. Cope Award of the ACS (2009), the Robert Robinson Award of the Royal Society of Chemistry (2012), and the Roger Adams Award of the ACS and the Foresight Feynman Theory Award in 2021.
Houk was a Camille and Henry Dreyfus Teacher-Scholar and an Alfred P. Sloan Foundation Fellow, a Fellow of the AAAS, the ACS, the WATOC and in 2012, he became a Fellow of the Royal Society of Chemistry. He was elected to the American Academy of Arts and Sciences (2002), the International Academy of Quantum Molecular Sciences (2003) and elected a member of the National Academy of Sciences in 2010. Houk has served on the advisory boards of the Chemistry Division of the National Science Foundation, the ACS Petroleum Research Fund and for a variety of journals, including, among others, Accounts of Chemical Research, the Journal of the American Chemical Society and the Journal of Organic Chemistry. He was the North American co-chair of Chemistry – A European Journal and he was a senior editor of Accounts of Chemical Research from 2005–15.
Houk is an authority on theoretical and computational organic chemistry. His group is involved in developments of rules to understand reactivity, computer modeling of complex organic reactions and experimental tests of the predictions of theory. He collaborates prodigiously with chemists all over the world. Among his current interests are the theoretical investigations and design of enzyme-catalyzed reactions, the quantitative modeling of asymmetric reactions used in synthesis, and the mechanisms and dynamics of pericyclic reactions and competing diradical processes. He has published over 1444 articles in refereed journals and has an h-index of 141.
- Information about 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).
- 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"
2019
Professor Gregory C. Fu - California Institute of Technology "Nucleophilic Substitution Reactions: A Radical Alternative to SN1 and SN2 Reactions"
John F. Hartwig - University of California, Berkeley
"Selective, Catalytic Functionalization of C-H Bonds with Small and Large Catalysts"
2021
Professor Vern L. Schramm - Albert Einstein College of Medicine
"Enzymatic Transition States and Transition State Analogues"
2022
Karen Goldberg - University of Pennsylvania
"Molecular Oxygen as a Reagent in Late Transition Metal Organometallic Chemistry"
