Advances in Physical Organic Chemistry, Volume 40 (Advances in Physical Organic Chemistry)

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 applications from biology to solid state physics. This text is ideal for those interested in the relationship between the structure and function of organic compounds, including physical and theoretical chemists as well as organic and bioorganic chemists. Editor's preface.pdf 1 Editor's preface 1 Subject Index.pdf 3 Contributors to Volume 40.pdf 11 Contributors to Volume 40 11 Finite molecular assemblies in the organic solid state-toward engineering properties of solids.pdf 12 Finite molecular assemblies in the organic solid state: toward engineering properties of solids 12 Introduction 12 Finite molecular assemblies 13 Supramolecular synthons, finite assemblies, and functional solids 15 Finite assemblies in the solid state 16 Synthons 17 Synthetic assemblies 17 Two-component assemblies 17 1D assemblies 21 2D assemblies 22 3D assemblies 26 Functional assemblies 26 Two-component assemblies 26 1D assemblies 32 2D assemblies 33 3D assemblies 39 Our approach: template-controlled solid-state reactivity 46 Linear templates 47 Target-oriented syntheses 49 Summary and outlook 51 Acknowledgment 52 References 52 Mechanisms of hydrolysis and rearrangements of epoxides.pdf 56 Mechanisms of hydrolysis and rearrangements of epoxides 56 Introduction 57 Limiting mechanisms of epoxide reactions 57 Mechanisms of hydrolysis of epoxides derived from simple alkenes and cycloalkenes 59 Kinetic studies 59 Acid-catalyzed hydrolysis of aliphatic epoxides 60 Simple primary and secondary epoxides 60 Simple tertiary epoxides 61 pH-independent and hydroxide ion-catalyzed hydrolyses of aliphatic primary and secondary epoxides 63 Acid-catalyzed hydrolyses of alkyl- and vinyl-substituted epoxides 63 Relative reactivities 63 Simple vinyl epoxides 64 Cyclic vinyl epoxides 66 Mechanisms of hydrolysis of styrene oxides 67 Acid-catalyzed hydrolysis of styrene oxides 67 Substituent effects on addition of amines and hydroxide ion to styrene oxides 71 Substituent effects on the pH-independent reactions of styrene oxides 72 Mechanisms of acid-catalyzed hydrolysis of 1-phenylcyclohexene oxides, indene oxides and 1,2,3,4-tetrahydronaphthalene-1,2-epoxides 73 Acid-catalyzed hydrolysis of 1-phenylcyclohexene oxides 73 Acid-catalyzed hydrolysis of indene oxides: transition-state effects on stereochemistry of diol formation 75 Tetrahydronaphthalene epoxide hydrolysis: conformational effects on stereochemistry of diol formation 76 General acid catalysis in epoxide reactions 80 Ethylene oxide and simple primary and secondary epoxides 80 Tertiary epoxides 81 Acetals and epoxy ethers 81 Vinyl epoxides 82 Benzylic epoxides and arene oxides 83 pH-independent reactions of epoxides 86 Simple alkyl epoxides 86 Arene oxides 86 Cyclic vinyl epoxides 88 Benzylic epoxides that undergo rate-limiting 1,2-hydrogen migration 89 Benzo[a]pyrene 7,8-diol 9,10-epoxides 90 Summary of pH-independent mechanisms 92 Epoxide isomerization accompanying pH-independent reactions 92 Benzylic epoxides that exhibit complicated pH-rate profiles 95 Precocene I 3,4-oxide 95 Benzo[a]pyrene 7,8-diol 9,10-epoxide (80) 97 Specific effects of chloride ion in epoxide hydrolysis 99 Partitioning of hydroxycarbocations 100 Overall summary 103 Acknowledgments 103 References 104 Mechanistic studies on enzyme-catalyzed phosphoryl transfer.pdf 108 Mechanistic studies on enzyme-catalyzed phosphoryl transfer 108 Introduction 109 Mechanistic possibilities for phosphoryl transfer 110 Nomenclature issues 112 Uncatalyzed reactions of phosphomonoesters 112 Dianions of phosphomonoesters 113 Monoanions of phosphomonoesters 117 Uncatalyzed reactions of phosphodiesters 119 Uncatalyzed reactions of phosphotriesters 123 Implications for enzymatic catalysis 125 Enzymes that catalyze transfer of the phosphoryl (PO3) group 129 Phosphatases: general 129 Alkaline phosphatase 129 Acid phosphatase 133 Purple acid phosphatases 134 Ser/Thr protein phosphatases 138 Protein-Tyrosine Phosphatases (PTPASES) 142 Ras 147 Phosphoglucomutases 150 Phosphodiesterases 153 Staphylococcal nuclease 153 Ribonuclease (RNASE) 154 Phosphotriesterases 156 References 160 The physical organic chemistry of very high-spin polyradicals.pdf 168 The physical organic chemistry of very high-spin polyradicals 168 Introduction 168 Exchange coupling and magnetism 170 Preparation and characterization of polyarylmethyl polyradicals 176 High-spin versus low-spin polyradicals 178 Diradicals 178 Triradicals 184 Tetraradicals 187 Diradical anions and diradical dianions 189 Star-branched and dendritic polyarylmethyl polyradicals 190 Design of very high-spin polyradicals 192 Defects 192 Macrocyclic octaradical and annelated macrocyclic tetradecaradical 194 Organic spin clusters 195 Dendritic-macrocyclic polyradicals 196 Macrocyclic-macrocyclic polyradicals 199 Annelated macrocyclic polyradicals 201 Very high-spin polyarylmethyl polymers 203 Conclusion and outlook 208 Acknowledgements 208 References 208 Carbenes generated within cyclodextrins and zeolites.pdf 215 Carbenes generated within cyclodextrins and zeolites 215 Introduction 215 Guest@host 215 Definition of guest@host 215 Supramolecular chemistry 216 Characterizing the IC 217 Guests 217 Neutral organic reaction intermediates 217 1,3-Cyclobutadiene 217 Ortho-benzyne 217 Carbenes 218 Hosts 218 Cyclodextrins 218 Structure and stoichiometry 218 Zeolites 219 Faujasite structure and stoichiometry 219 Choice of hosts 220 - and -CyDs 221 NaY FAU 221 Objectives 221 Shape selectivity 221 Steering reaction outcomes 222 Control carbene spin state 223 Carbene bond angle distortion 223 Facilitate intersystem-crossing 224 Control intramolecular reactions 224 Constraint 224 Topologic distortion 224 Inhibit intermolecular reactions 224 Limit guest mobility 225 Supramolecular carbene chemistry 225 Carbene reactions 225 Phase transfer catalysis 225 CyD-mediated Reimer-Tiemann reaction 225 CyD derivatization using nitrogenous carbene precursors 226 Encapsulated methylene 227 Choice of carbenes 228 Case studies 228 2-Adamantanylidene 229 2-Methylcyclohexanylidene 231 Evidence for diazo compound intermediacy 231 No increased C-H insertion into methyl group 232 Alkene isomer ratio unchanged 233 Cyclooctanylidene 235 3-Nortricyclanylidene 236 Phenylcarbene 242 Chloro(phenyl)carbene 242 Photolysis in alcohol solution 243 Photolysis in the supramolecular phase 244 Conclusions 251 Acknowledgments 252 References 252 Computer modeling of enzyme catalysis and its relationship to concepts in physical organic chemistry.pdf 262 Computer modeling of enzyme catalysis and its relationship to concepts in physical organic chemistry 262 Introduction 262 Formulating chemical reactivity in solutions and in enzymes in a computationally convenient way; the empirical valence bond and other QM/MM methods 264 The EVB as a basis for LFER in solutions and enzymes 269 Proton transport in carbonic anhydrase as an example of the difference between microscopic and phenomenological LFERs 273 Protein reorganization energy and the preorganization concept 279 Applying our concepts to different catalytic proposals 282 The desolvation proposal and the assumption that enzyme active sites are nonpolar 283 The near attack conformation proposal 286 The low-barrier hydrogen bond proposal can be best examined by using VB concepts 290 Dynamical proposals and misunderstandings of the static nature of the reorganization energy 294 Tunneling and related effects 297 Concluding remarks 299 Acknowledgments 299 References 300 Cumulative Index of Authors.pdf 307 Cumulative Index of Authors 307 Cumulative Index of Titles.pdf 309 Cumulative Index of Titles 309 Author Index.pdf 319 Content: Editor's preface Pages ix-x Contributors to Volume 40 Pages xi-xi Carbenes generated within cyclodextrins and zeolites Review Article Pages 1-47 Murray G. Rosenberg, Udo H. Brinker Mechanistic studies on enzyme-catalyzed phosphoryl transfer Review Article Pages 49-108 Alvan C. Hengge Finite molecular assemblies in the organic solid state: toward engineering properties of solids Review Article Pages 109-152 Tamara D. Hamilton, Leonard R. MacGillivray The physical organic chemistry of very high-spin polyradicals Review Article Pages 153-199 Andrzej Rajca Computer modeling of enzyme catalysis and its relationship to concepts in physical organic chemistry Review Article Pages 201-245 Sonja Braun-Sand, Mats H.M. Olsson, Arieh Warshel Mechanisms of hydrolysis and rearrangements of epoxides Review Article Pages 247-298 Dale L. Whalen Author Index Pages 299-313 Cumulative Index of Authors Pages 315-316 Cumulative Index of Titles Pages 317-326 Subject Index Pages 327-334