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Advances in Physical Organic Chemistry
1st Edition - December 12, 2002
Editors: Thomas Tidwell, John P. Richard
Hardback ISBN:
9 7 8 - 0 - 1 2 - 0 3 3 5 3 7 - 4
Advances in Physical Organic Chemistry provides the chemical community with authoritative and critical assessments of the many aspects of physical organic chemistry. The field is… Read more
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Advances in Physical Organic Chemistry provides the chemical community with authoritative and critical assessments of the many aspects of physical organic chemistry. The field is a fast developing one, with results and methodologies finding application from biology to solid state physics.
This latest volume deals comprehensively with investigations that can be traced back to the birth of the field but which are still proving critical to the understanding of the stability of organic molecules and the mechanisms for their reactions.
- Volume 37 of this hugely successful Advances in Physical Organic Chemistry series
- Comprehensive review articles covering various topics of interest within the physical organic chemistry field
For organic and physical chemists and biochemists.
Introduction.
Quantitative thermodynamic criteria of stability in the gas phase. Definitions and experimental techniques. The specific case of carbocations.
Theoretical calculations.
Uncertainties.
Thermodynamics and structure of selected species. Carbocations C1 to C4. Aliphatic carbocations with more than five carbon atoms. Cyclic species without formal systems. Cyclopropyl-substituted carbonations. Secondary and tertiary carbocations derived from cage hydrocarbons. Carbenium ions with formal systems. Two-electron aromatic and homoaromatic ions. Six-electron aromatic ions. Phenyl-substituted carbocations.
Solution reactivity. Thermodynamic properties. Reaction kinetics.
- No. of pages: 373
- Language: English
- Published: December 12, 2002
- Imprint: Academic Press
- Hardback ISBN: 9780120335374
TT
Thomas Tidwell
Affiliations and expertise
University of Toronto, Ontario, CanadaJR
John P. Richard
John Richard received his Ph.D. from Ohio State University, under the direction of Perry Frey. His thesis reported the synthesis of chiral oxygen-18 labelled phosphorothioate analogs of adenine nucleotides, and their use to determine the stereochemical course for enzyme-catalyzed phosphoryl transfer reactions. He worked as a postdoctoral fellow at Brandeis University with Bill Jencks, and developed an azide ion clock to measure the lifetimes of carbocation intermediates of solvolysis reactions. This clock was used to show that the mechanism for nucleophilic substitution reactions at ring-substituted 1 phenylethyl derivatives is controlled by the lifetimes of the carbocation intermediates of the solvolysis reaction. He began his independent career at the Department of Chemistry at the University of Kentucky in 1985 and moved to SUNY Buffalo in 1993.
Richard is interested in understanding the mechanism for the reactions of small molecules in water, and for their catalysis by enzymes. His early independent studies focused on developing methods to determine rate and equilibrium constants for reactions of simple carbanions and carbocations intermediates of organic reactions in water. This led to a broad characterization of substituent effects on the stability of these intermediates, and a rationale for the observation that many polar electron-withdrawing substituents cause a decrease in both the stability and reactivity of resonance stabilized carbocations. Richard transitioned to studies on the mechanism for small molecule catalysis in models for enzyme-catalyzed reactions. These included proton transfer, hydride transfer, aldol condensation reactions, and phosphate diester hydrolysis. Most recently he has focused on determining the mechanism for the stabilization of reactive carbocation and carbanion enzymatic reaction intermediates through interactions with active-site protein side chains. An important outcome of this work is the determination that the most proficient enzyme catalysts of metabolic reactions utilize substrate binding interactions as glue in the construction of protein-substrate cages that provide a tremendous stabilization of carbanion and carbocation reaction intermediates. These results provide a simple rational for the existence of enzyme catalysts that follow Koshland's induced-flt mechanism.
Affiliations and expertise
Department of Chemistry, University of Buffalo, NY, USA