This course will examine
the tools - both theoretical and experimental - that the modern organic
chemist has at his or her disposal for elucidating mechanisms.
Anslyn, E. V.; Dougherty,
D. A. Modern Physical Organic Chemistry. University Science Books,
Useful References, Not Required:
Sundberg, R. J.; Carey, F.
A. Advanced Organic Chemistry, Part A: Structure and Mechanism,
4th Edition. Kluwer/Plenum Press, 2000.
Gomez-Gallego, M.; Sierra,
M. A. Organic Reaction Mechanisms - 40 Solved Cases. Springer,
Isaacs, N. Physical Organic
Chemistry, 2nd Edition, Addison-Wesley-Longman, 1995.
Fleming, I. Frontier Orbitals
and Organic Chemical Reactions. Wiley, 1996.
Carpenter, B. K. Determination
of Organic Reaction Mechanisms. Wiley, 1994
Smith, M. B.; March, J.
March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure,
5th Edition. Wiley, 2000.
Lowry, T. H.; Richardson,
K. S. Mechanism and Theory in Organic Chemistry, 3rd Edition.
Harper Collins, 1987.
Quinkert, G.; Egert, E.;
Griesinger, C. Aspects of Organic Chemistry: Structure. VCH,
Moss, R. A.; Platz, M. S.;
Jones, M. Reactive Intermediate Chemistry. Wiley, 2004.
Eliel, E. L.; Wilen, S.
H. Stereochemistry of Organic Compounds. Wiley, 1994.
Young, D. Computational
Chemistry: A Practical Guide for Applying Techniques to Real World Problems.
Source of Practice Problems:
Glossary of Terms Used in Physical Organic Chemistry:
A working knowledge of undergraduate
Organic Chemistry is expected.
This class is not about memorization.
It is about developing analytical thinking and problem solving skills.
By the end of the quarter,
I expect the following:
When given an experimental
observation on a particular reaction, you should be able to:
(1) write down a reasonable
arrow-pushing mechanism for the reaction
(2) decide whether existing
theories can explain the observed reactivity
(3) design experiments
to test your proposed mechanism/explanation
(4) evaluate the validity/plausibility
of others' explanations
(subject to change):
I. Point Group Symmetry
symmetry elements, operations,
and point groups
chirality and topicity
symmetry as mechanistic tool
symmetry and efficiency
II. Intro to Arrow-Pushing
typical reactivity patterns
for various reactive intermediates
III. Kinetics and Thermodynamics
types of energy
potential energy surfaces
intro to chemical kinetics
kinetic vs. thermodynamic
dynamics and tunneling
Hammond postulate and Curtin-Hammett
linear free energy relationships
IV. Molecular Orbital
what does the Schrodinger
simple Huckel theory: doing
quantum mechanics by hand!
frontier orbital concepts
V. Noncovalent Interactions
and Supramolecular Chemistry
types of noncovalent interactions
as an independent field
preorganization and templating
incarceration and mechanical
devices, sensors and machines
interactions in transition
VI. Conformational Analysis
sterics, strain, electronics,
orbital (e.g. anomeric)
polar effects (H-bonding,
transition state effects
- models for selectivity in organic reactions
VII. Reactive Intermediates
and Reactivity Redux
acidity, basicity, philicity
carbenes and other
other weird wild stuff