<p>Preface for Volumes 1–3 XV</p> <p>Introduction: Definitions of Catalysis XXI</p> <p><b>Volume 1</b></p> <p><b>1 From Catalysis to Lewis Base Catalysis with Highlights from 1806 to 1970 1</b><br /><i>Edwin Vedejs</i></p> <p>1.1 Introduction 1</p> <p>1.2 Catalysis 1</p> <p>1.3 Progress with Catalysis in Organic Chemistry 3</p> <p>1.4 Ostwald’s Redefinition of Catalysis 5</p> <p>1.5 The First Example of Lewis Base Catalysis 7</p> <p>1.6 The Road to Mechanistic Comprehension; Multistage Catalysis by Lewis Base 9</p> <p>1.7 An Uneven Path to a Unifying Concept 12</p> <p>1.8 Amine Catalysis 17</p> <p>1.9 Summary 26</p> <p><b>Section I Principles 31</b></p> <p><b>2 Principles, Definitions, Terminology, and Orbital Analysis of Lewis Base–Lewis Acid Interactions Leading to Catalysis 33</b><br /><i>Scott E. Denmark and Gregory L. Beutner</i></p> <p>2.1 Introduction 33</p> <p>2.2 Lewis Definitions of Valence and the Chemical Bond 34</p> <p>2.3 Extensions, Expansions of, and Objections to the Lewis Definitions 35</p> <p>2.4 Interpretation of the Lewis Definitions in the Idiom of Molecular Orbital Theory and Quantum Mechanics 38</p> <p>2.5 Defining Lewis Base Catalysis 40</p> <p>2.6 Theoretical Analysis of the Geometrical and Electronic Consequences of Lewis Acid–Lewis Base Interactions 44</p> <p>2.7 Summary 51</p> <p><b>3 Thermodynamic Treatments of Lewis Basicity 55</b><br /><i>Jean-François Gal</i></p> <p>3.1 Introduction 55</p> <p>3.2 Basic Thermodynamics for the Study of Lewis Acid–Base Interactions 56</p> <p>3.3 Scales of Lewis Affinity and Basicity 58</p> <p>3.4 Lewis Acidity and Lewis Basicity: Thermodynamic Scales 62</p> <p>3.5 Quantum Chemical Tools 74</p> <p>3.6 Conclusion and Overview 75</p> <p>3.7 Summary 76</p> <p>List of Abbreviations 77</p> <p><b>4 Quantitative Treatments of Nucleophilicity and Carbon Lewis Basicity 85</b><br /><i>Sami Lakhdar</i></p> <p>4.1 Introduction 85</p> <p>4.2 Nucleophilicity 85</p> <p>4.3 Lewis Basicity 91</p> <p>4.4 Nucleofugality 93</p> <p>4.5 Selected Applications 95</p> <p>4.6 Conclusion 113</p> <p>4.7 Summary 113</p> <p><b>Section II Mechanism and Lewis Base Catalysis: Nucleophilicity Is Only Part of the Story 119</b></p> <p><b>5 Anhydride Activation by 4-Dialkylaminopyridines and Analogs 121</b><br /><i>Raman Tandon and Hendrik Zipse</i></p> <p>5.1 Historical Background 121</p> <p>5.2 Mechanistic Considerations 121</p> <p>5.3 Catalyst Structure and Variation 124</p> <p>5.4 The Influence of Reaction Conditions 130</p> <p>5.5 The Influence of Acyl Donors 132</p> <p>5.6 The Influence of Substrate Structure 136</p> <p>5.7 Summary 141</p> <p><b>6 Mechanistic Understanding of Proline Analogs and Related Protic Lewis Bases 145</b><br /><i>Alan Armstrong and Paul Dingwall</i></p> <p>6.1 Proline Catalysis: Overview 145</p> <p>6.2 Mechanism of the Proline-Catalyzed Aldol Reaction 147</p> <p>6.3 Mechanism of the Proline-Catalyzed α-Amination and α-Aminoxylation Reactions 161</p> <p>6.4 The Proline-Mediated Conjugate Addition Reaction 170</p> <p>6.5 Modified Proline Derivatives 175</p> <p>6.6 Concluding Remarks 186</p> <p><b>7 Mechanistic Options for the Morita–Baylis–Hillman Reaction 191</b><br /><i>Marilia S. Santos, José Tiago M. Correia, Ana Paula L. Batista, Manoel T. Rodrigues Jr., Ataualpa A. C. Braga, Marcos N. Eberlin, and Fernando Coelho</i></p> <p>7.1 The Morita–Baylis–Hillman Reaction: An Overview 191</p> <p>7.2 Kinetic Studies Applied to aza-Morita–Baylis–Hillman Reaction 195</p> <p>7.3 Theoretical Calculations Applied to MBH Reaction 208</p> <p>7.4 Mass Spectrometry Aid the Understanding of the Morita–Baylis–Hillman Reaction 217</p> <p>7.5 Classical and Nonclassical Methods for Mechanistic Studies Associated with the Morita–Baylis–Hillman Reaction: Which Is the Correct Pathway of This Reaction? 226</p> <p><b>8 Mechanism of C-Si Bond Cleavage Using Lewis Bases 233</b><br /><i>Hans J. Reich</i></p> <p>8.1 Introduction 233</p> <p>8.2 Mechanistic Issues 235</p> <p>8.3 Alkylation 247</p> <p>8.4 Benzylation 253</p> <p>8.5 Allylation 255</p> <p>8.6 Allenylation/Propargylation 260</p> <p>8.7 Alkynylation 261</p> <p>8.8 Arylation 262</p> <p>8.9 Vinylation 263</p> <p>8.10 Cyanation 264</p> <p>8.11 Summary 275</p> <p><b>9 Bifunctional Lewis Base Catalysis with Dual Activation of X3Si-Nu and C=)O 281</b></p> <p>9.1 Addition of Allyltrichlorosilanes to Aldehydes 281</p> <p>9.2 Aldol Additions of Trichlorosilyl Enol Ethers Derived from Ketones, Aldehydes, and Esters 293</p> <p><b>10 Bifunctional Lewis Base Catalysis with Dual Activation of R–M and C=O 339</b></p> <p>10.1 Introduction 339</p> <p>10.2 Activation of C–Zn and Related C–Mg by a Simple Lewis Base 340</p> <p>10.3 Lewis Base-Activated C–Zn + C</p> <p>10.4 Role of Dimeric Organozinc Species 345</p> <p>10.5 Scope of Carbonyl Substrates in Catalytic Asymmetric Organozinc Addition Reaction 350</p> <p>10.6 Anionic Lewis Base Activation in Mg(II) and Zn(II) Ate Complexes 372</p> <p>10.7 Summary 382</p> <p><b>11 The Corey–Bakshi–Shibata Reduction: Mechanistic and Synthetic Considerations – Bifunctional Lewis Base Catalysis with Dual Activation 387</b><br /><i>Christopher J. Helal and Matthew P. Meyer</i></p> <p>11.1 Introduction 387</p> <p>11.2 The Catalytic Cycle 389</p> <p>11.3 Mechanism 393</p> <p>11.4 Applications of the CBS Reduction in Organic Synthesis 416</p> <p><b>Volume 2</b></p> <p><b>Section III Applications: Lewis Base Catalysis Involving an Activation Step 457</b></p> <p>12 Chiral Lewis Base Activation of Acyl and Related Donors in Enantioselective Transformations 459<br /><i>James I. Murray, Zsofia Heckenast, and Alan C. Spivey</i></p> <p>13 Catalytic Generation of Ammonium Enolates and Related Tertiary Amine-Derived Intermediates: Applications, Mechanism, and Stereochemical Models 527<br /><i>Khoi N. Van, Louis C. Morrill, Andrew D. Smith, and Daniel Romo</i></p> <p>14 Morita–Baylis–Hillman, Vinylogous Morita–Baylis–Hillman, and Rauhut–Currier Reactions 655<br /><i>Allison M. Wensley, Nolan T. McDougal, and Scott E. Schaus</i></p> <p>15 Beyond the Morita–Baylis–Hilman Reaction 715<br /><i>Yi Chiao Fan and Ohyun Kwon</i></p> <p>16 Iminium Catalysis 805<br /><i>Aurélie Claraz, Juha H. Siitonen, and Petri M. Pihko</i></p> <p>17 Enamine-Mediated Catalysis 857<br /><i>John J. Murphy, Mattia Silvi, and Paolo Melchiorre</i></p> <p><b>Volume 3</b></p> <p><b>Section IVa Applications: Enhanced Nucleophilicity by Lewis Base Activation 903</b></p> <p>18 Si-C-X and Si-C-EWG as Carbanion Equivalents under Lewis Base Activation 905<br /><i>Ping Fang, Chang-Hua Ding, and Xue-Long Hou</i></p> <p>19 Activation of B-B and B-Si Bonds and Synthesis of Organoboron and Organosilicon Compounds through Lewis Base-Catalyzed Transformations 967<br /><i>Amir H. Hoveyda, Hao Wu, Suttipol Radomkit, Jeannette M. Garcia, Fredrik Haeffner, and Kang-sang Lee</i></p> <p><b>Section IVb Applications: Enhanced Electrophilicity and Dual Activation by Lewis Base Catalysis 1011</b></p> <p>20 Lewis Base-Catalyzed Reactions of SiX3-Based Reagents with C</p> <p>21 Lewis Base-Catalyzed, Lewis Acid-Mediated Reactions 1039<br /><i>Sergio Rossi and Scott E. Denmark</i></p> <p>22 Lewis Bases as Catalysts in the Reduction of Imines and Ketones with Silanes 1077<br /><i>Pavel Kočovský and Andrei V. Malkov</i></p> <p>23 Reactions of Epoxides 1113<br /><i>Tyler W. Wilson and Scott E. Denmark</i></p> <p><b>Section V Lewis Base-Catalyzed Generation of Electrophilic Intermediates 1153</b></p> <p>24 Lewis Base Catalysis: A Platform for Enantioselective Addition to Alkenes Using Group 16 and 17 Lewis Acids 1155<br /><i>Dipannita Kalyani, David J.-P. Kornfilt, Matthew T. Burk, and Scott E. Denmark</i></p> <p><b>Section VI Bifunctional (and Multifunctional) Catalysis 1213</b></p> <p>25 Bifunctional and Synergistic Catalysis: Lewis Acid Catalysis and Lewis Base-Assisted Bond Polarization 1215<br /><i>Won-jin Chung and Scott E. Denmark</i></p> <p>26 Bifunctional Catalysis with Lewis Base and X-H Sites That Facilitate Proton Transfer or Hydrogen Bonding 1259<br /><i>Curren T. Mbofana and Scott J. Miller</i></p> <p><b>Section VII Carbenes: Lewis Base Catalysis Triggers Multiple Activation Pathways 1289</b></p> <p>27 Catalysis with Stable Carbenes 1291<br /><i>Darrin M. Flanigan, Nicholas A. White, Kevin M. Oberg, and Tomislav Rovis</i></p> <p>Summation 1351</p> <p>Index 1355</p>