Our research focuses on the application of computational methods to the study of organic reactivity in diverse environments (in the gas phase, in solution, in the interiors of biological macromolecules, as part of organometallic complexes). The intimate relationship between theory and experiment pervades each of these endeavors, and a focus of our work is the design of molecular architectures with unusual reactivity.


"Playfulness is an incentive for the scientist and a motor of progress."

- Rolf Huisgen, The Adventure Playground of Mechanisms and Novel Reactions, 1994.


"Don't ask yourself what the world needs. Ask yourself what makes you come alive and then go do that. Because what the world needs is people who have come alive."

- Howard Thurman


Reaction Design and Theories of Reactivity



Post-Transition State Bifurcations

Transition State Complexation

Concerted Asynchronous Reactions

Reactive Intermediate Promoted Polycyclization (RIPP) Reactions

Hiscotropic Rearrangements

Pericyclic Perspectives


Theoretical Bioorganic and Bioinorganic Chemistry



Complexity Creation in Bio- and Biomimetic Syntheses of Natural Products


Nonclassical Cations in Biology

Terpenoid Biosynthesis

Sulfur in Biology

Biosynthetic Dipolar Cycloadditions

Computing Chemical Shifts to Aid Natural Product Structure Elucidation

Hydration of Biologically Active Compounds

Ladderane Lipids

Drug Design: Conformational Analysis, Docking, and Library Design

Noncovalent Catalysis of Biological Decarboxylations

Antibody Catalyzed Organic Reactions

Biosynthesis and Molecular Pharmacology of Nitric Oxide and Nitroxyl


Predicting Spectra



. NMR chemical shifts and Coupling Constants

. Mass Spectra


Chemical Education



Making Computational Chemistry Accessible to the Blind & Visually Impaired

3D Printing

Dynamics Trajectory Movies

Historical Chemistry


Organic Molecules with Unusual Properties



Sulfur-Lone Pair Interactions

5-Center 4-Electron Cations and Their Relatives

Unusual Oxonium Cations



Sigmatropic Shiftamers


Fickle Hexadienes

Tetrathiafulvalenes under Extreme Conditions


Physical Organometallic Chemistry



Metal-Promoted Sigmatropic Shifts

Dirhodium Tetracarboxylate-Promoted Reactions

Iron-Promoted Electrocyclic Reactions

Interactions of Chromium Arenes with Reactive Intermediates


Rates, Regio- and Stereoselectivity of Synthetically Useful Reactions




Schmidt Rearrangements

Radical Cation Diaza-Cope Rearrangements

Oxidopyrilum Zwitterion + Alkene Cycloadditions

Nazarov Electrocyclizations

Reactivity of Enamines and Iminium Ions Built from Aziridines

Dissecting Dyotropic Rearrangements

Lewis Acid Promoted Tandem Sigmatropic Shifts/Aromatic Substitutions

Diazocinone-forming Cascades

Semibullvalene Bromination

The Cationic Cascade Route to Longifolene

Rearrangements of Housane Radical Cations

Stereoselectivity of Intramolecular Diels-Alder Reactions

Regio- and Stereoselectivity of alpha-Lactam Ring-Opening Reactions



"If you don't know the past, how can you know the future?"

- Tony Bennett


"...it is through training in pure research that the mind is best prepared to capitalize broadly on chances as they arise... My area, physical organic chemistry, is a highly interdisciplinary pursuit that provides the principles for the design and synthesis of organic molecules with the goal of uncovering the origins of their structure and properties. It is the conceptual basis for the modern arenas of stereoselective, biomimetic, and materials chemistry. It provides basic tools for medicinal, environmental, and biological chemistry. So, why is physical organic chemistry viewed as off-limits to young scientists who have hopes of establishing research funding? What spoiled the passion for such a central theme in chemistry? Could it be that 'visionaries' who 'knew the way' were allowed to project their futures on that of the field without regard for diversity?"

- Jay Siegel, C&EN, March 26, 2001, p.114


"..the compounds just described [(C5H5)2MX2, M = V, Nb, Ta, X = Cl, Br] were the lineal ancestors of today's marvelous so-called single-site catalysts for olefin polymerization. They were discovered, I would like to emphasize, not by people who had written a grant proposal to work on olefin polymerization, but by people who were funded to do fundamental research that had no predictable practical use."

- F. A. Cotton, J. Organomet. Chem. 2001, 637-639, 18-26


"It has always seemed to me that the most attractive applications of theory are to explore the unknown. If you want to find something truly new, your chances are better if you look in new places."

- Paul Schleyer, J. Comp. Chem. 2001, 13, ix-xi


"Every attempt to employ mathematical methods in the study of chemical questions must be considered profoundly irrational and contrary to the spirit of chemistry."

- Auguste Compte, Philosophie Positive 1830