Advances in physical organic chemistry 2015/ edited by Ian H. Williams and Nicholas H. Williams

1. Metal Ion-Promoted Leaving Group Assistance In the Light Alcohols 1
R. Stan Brown
1. Introduction 2
2. Metal Ion-Promoted LGA 5
3. Metal Ion-Promoted Alcoholysis of Phosphates 15
4. LGA Provided by Metal Ions in the Acyl Transfer from Amides, Ureas,
and Carbamates to Solvent ROH 38
5. Conclusions and Speculations 48
Acknowledgments
References
2. Medium Effects in Biologically Related Catalysis 57
Marcello Forconi
1. Introduction
2. Phosphoryl Transfer Reactions 60
3. Solvent Effects in Sulfuryi Transfer Reaaions 75
4. Solvent Effects in Sn2 Reactions ofS-Adenosyimethionine 76
5. Decarboxyiation Reactions 79
6. Kemp Elimination
7. Conclusions and Implications for Bioinspired Catalysis 93
Acknowledgments ^
References ^
3. Combustion Pathways of Biofuel Model Compounds: AReview
of Recent Research and Current Challenges Pertaining to First-,
Second-, and Third-Generation Biofuels 103
Carrigan J. Hayes, Donald R. Burgess, Jr., Jeffrey A. Manion
1. Introduction
2. Overview ofFirst-Generation Biofuels and Their Model Compounds 118
3. Overview ofSecond-Generation Biofuels and Their Model Compounds 135
4. Overview ofThird- and Fourth-Generation Biofuels 163
5. Challenges in Biofuel Combustion Engineering 165
6. Conclusion 168
References 169
4. Mechanistic Perspectives on Stereocontrol in Lewis
Acid-Mediated Radical Polymerization: Lessons from
Small-Molecule Synthesis 189
Benjamin B. Noble and Michelle L. Coote
1. Introduction 190
2. Important Features of Radical Reactivity 194
3. Radical Polymerization 200
4. Lewis Acids in Radical-Based Polymer Synthesis 208
5. Synthetic Radical Transformations 216
6. Lewis Acids In Radical-Based Synthetic Transformations 219
7. Some Lessons from Synthesis 235
8. Conclusion 246
Acknowledgments 247
References 247
Subject Index 259
Author Index 269
Cumulative Index of Titles 287
Cumulative Index of Authors 299