J. Peter Guthrie
Professor
B.Sc., University of Western Ontario
Ph.D. Harvard
Room 222, Chemistry Building
(519) 661-2111, ext. 86352
Computational Organic Chemistry. Rates and equilibria of organic
reactions, including aldol and Claisen condensations and Michael
reactions. Calculation of rate constants by No Barrier Theory
Awards:
• CIC Medal
• Distinguished Research Professor
• Alfred Bader Award in Organic Chemistry
• Fellow of the Royal Society of Canada
• Killam Fellow
• Syntex Award
• Bucke Science Prize of the University of Western Ontario
• Steacie Fellow
• Sloan Fellow
Current Research Programs:
• Prediction of rate constants for reactions in solution;
I have found a way to predict the absolute rate constants for chemical reactions in solution by a quite general
method which seems intuitively reasonable and is computationally facile, at least in many cases.
This method involves no adjustable parameters, and requires no input of kinetic information.
The fundamental idea is that the kinetic barrier to a chemical reaction arises because of the need to have several
things (molecular events) occur simultaneously in order for the reaction to take place. If only one thing had to
happen then there would be no barrier and the energy would be a simple quadratic function of the extent of progress
along the reaction coordinate. Because most real reactions require two or more processes, each associated with a
quadratic barrier, in order to give the overall transformation, the overall process is seen to have a barrier.
This model permits calculation of the barrier if the energy changes for the simple processes can be estimated.
For many classes of reaction this is possible, and for the cases examined so far the method leads to good
approximations to the observed free energies of activation. Computational methods are now sufficient to allow
free energy changes to be calculated using molecular orbital theory.
I propose to apply the method to a selection of reactions, ultimately covering all of chemistry, to test whether
it is indeed general and reliable. For this to be practical requires developing computer programs to automate
the process.
This research will have an impact on many areas of chemistry and enzymology, and will lead to methods providing
useful guidance to synthetic chemists, both academic and industrial.
Selected Publications: Guthrie, J.P., Peiris, S., Simkin, M. and Wang, Y., “Rate constants for decarboxylation reactions calculated using No Barrier Theory”, Can. J. Chem. 2010, 88, 79-98. doi:10.1139/V09-164 Guthrie, J. P., "Alfred Bader Award Lecture 2003. Predicting the rates of chemical reactions", Can. J. Chem. 2005, 83, 1-8. doi: 10.1139/V04-172 Guthrie, J. P.; Pitchko, V., "Reactions of carbocations with water and azide ion: calculation of rate constants from equilibrium constants and distortion energies using No Barrier Theory", J. Phys. Org. Chem. 2004, 17, 548-559. DOI: 10.1002/poc.763 Guthrie, J. P., "No Barrier Theory: calculating rates of chemical reactions from equilibrium constants and distortion energies", ChemPhysChem 2003, 4, 809-816. DOI: 10.1002/cphc.200200327 Guthrie, J. P.; Pitchko, V., "Hydration of carbonyl compounds, an analysis in terms of No Barrier Theory. Prediction of rates from equilibrium constants and distortion energies.", J. Am. Chem. Soc. 2000, 122, 5520-5528. DOI: 10.1021/ja992991q
• Thermodynamics applied to organic reaction mechanisms;
• Measurement and prediction of equilibrium constants;
• Mechanistic organic chemistry;
• Computational methods for calculating rate and equilibrium constants in solution
