Advances in Physical Organic Chemistry

by John P. Richard (Editor)

Overview

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 rapidly developing one, with results and methodologies finding application from biology to solid state physics. - Reviews the application of quantitative and mathematical methods towards understanding chemical problems - Covers organic, organometallic, bioorganic, enzymes and materials topics

Product Details

ISBN-13:	9780123860484
Publisher:	Elsevier Science & Technology Books
Publication date:	09/12/2011
Series:	Advances in Physical Organic Chemistry , #45
Sold by:	Barnes & Noble
Format:	eBook
Pages:	272
File size:	10 MB

About the Author

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.

Table of Contents

Editor's Preface     ix
Contributors to Volume 42     xi
Cycloaromatization reactions: the testing ground for theory and experiment   Igor Alabugin   Boris Breiner   Mariappan Manoharan     1
Introduction: bonds lost and bonds formed, or chemical bookkeeping     1
Cycloaromatization reactions: breaking [pi]-bonds and breaking the rules     2
The diversity of cycloaromatization reactions     3
The relative role of [sigma]- versus [pi]-effects at the early reaction stage     6
[sigma]-Effects on reactant stability     10
[pi]-Effects on reactant stability     22
Transition state effects: communication of orthogonal orbitals in the transition state of radical-anionic cyclizations     23
Effects on product stability     27
Conclusion     31
References     31
N-Acyloxy-N-alkoxyamides - structure, properties, reactivity and biological activity   Stephen A. Glover     35
Introduction     35
Synthesis     39
Structure     43
Chemical reactivity     59
Biological activity of N-acyloxy-N-alkoxyamides     97
Conclusions     115
Acknowledgements     116
References     117
The Interplay between experiment and theory: computational NMR spectroscopy of carbocations   Hans-Ullrich Siehl     125
Introduction     125
Alkyl and cycloalkylmethyl cations     126
Vinyl cations     133
Cycloalkyl cations     142
[mu]-Hydrido-bridged carbocations     144
Bicyclic and polycyclic carbocations     145
[pi]-Stabilized carbocations     150
Heteroatom stabilized carbocations     156
Final remarks     158
Conclusions     160
Acknowledgments     160
References     160
Dynamics of guest binding to supramolecular systems: techniques and selected examples   Tamara C.S. Pace   Cornelia Bohne     167
Introduction     167
Techniques     169
Examples of supramolecular dynamics studies     185
Conclusions     216
Acknowledgements     217
References     217
Mechanisms of oxygenations in zeolites   Edward L. Clennan     225
Introduction     225
Zeolites     226
Experimental considerations     230
Intrazeolite photooxygenations     232
Acknowledgement     261
References     262
Metal-catalyzed alcoholysis reactions of carboxylate and organophosphorus esters   R. Stan Brown   Alexei A. Neverov     271
Introduction     271
Background theory     274
Titrations in alcohol     276
Metal ion alcoholysis and titration in alcohol     278
Transition metal ion and Ln[superscript 3+] catalysts of transesterifications of neutral carboxylate and organophosphate esters     284
Transition metal ion and La[superscript 3+]-catalysis of the alcoholysis of phosphate diesters     308
Conclusions     324
Acknowledgements     325
References     325
Author Index     333
Cumulative Index of Authors     351
Cumulative Index of Titles     353
Subject Index     363

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