Lewis Base Catalysis in Organic Synthesis, 3 Volume Set

Edwin Vedejs was born in 1941 in Riga, Latvia. After completion of his BS (University of Michigan, 1962) and PhD (University of Wisconsin, 1966), he spent a postdoctoral year with E. J. Corey at Harvard. Prof. Vedejs then joined the chemistry faculty at the University of Wisconsin (1967). In 1999, he returned to the University of Michigan as the Moses Gomberg Professor of Chemistry. Work in the Vedejs group combines topics at the interface of methodology, total synthesis, heterocycle chemistry, stereochemistry, and related mechanistic studies. Prof. Vedejs has won several awards: Alexander von Humboldt Senior Scientist Award, 1984; Professore a Contratto, University of Bologna, Italy, 1988; Helfaer Professor, 1991-1996 (UW); Pharmacia&Upjohn Teaching Award, 1996 (Chemistry Dept, UW). Robert M. Bock Professor (UW), 1997-98; Paul Walden Medal, Riga Technical University (1997); H. C. Brown Award for Creative Research in Synthetic Methods, 2004 (ACS). Grand Medal of the Latvian Academy of Sciences, 2005. Order of the Three Stars, Latvia, 2006. Honorary Doctorate, Riga Technical University 2010. Scott E. Denmark was born in New York on 17 June 1953. He obtained an S. B. degree from M.I.T. in 1975 and a D. Sc. Tech degree in 1980 from the ETH-Zürich under the direction of Professor Albert Eschenmoser. That same year he began his career as assistant professor at the University of Illinois. He was promoted to associate professor in 1986, full professor in 1987 and then in 1991 named the Reynold C. Fuson Professor of Chemistry. Professor Denmark?s research interests focus on the invention of new synthetic reactions and elucidating the origins of stereocontrol in novel, asymmetric transformations. He has pioneered the concept of chiral Lewis base activation of Lewis acids for catalysis in main group chemistry. His group has also developed palladium-catalyzed cross-couplings with organofunctional silicon compounds. In addition he is well-known for the development and application of tandem cycloadditions of nitroalkenes for the synthesis of complex natural and unnatural nitrogen containing compounds. In recent years, his group has investigated the use of chemoinformatics to identify and optimize catalysts for a variety of organic and organometallic reactions. Professor Denmark has won a number of honors for both research and teaching including: an NSF Presidential Young Investigator Award, A. C. Cope Scholar Award (ACS), Alexander von Humboldt Senior Scientist Award, Pedler Lecture and Medal (RSC), the ACS Award for Creative Work in Synthetic Organic Chemistry, the Yamada-Koga Prize, the Prelog Medal (ETH-Zürich), the H. C. Brown Award for Creative Research in Synthetic Methods (ACS), Robert Robinson Lecture and Medal (RSC), the ISHC Senior Award in Heterocyclic Chemistry, Paul Karrer Lectureship (Uni Zürich), the Frederic Stanley Kipping Award for Research in Silicon Chemistry (ACS), and the Harry and Carol Mosher Award (Santa Clara Section, ACS). He is a Fellow of the Royal Society of Chemistry and the American Chemical Society. He edited Volume 85 of Organic Syntheses, was Editor of Volumes 22-25 of Topics in Stereochemistry and was a founding Associate Editor of Organic Letters (1999-2004). After serving on the editorial board from 1994-2003, he became Editor in Chief and President of Organic Reactions, Inc. in 2008.

• Preface for Volumes 1–3 XVIntroduction: Definitions of Catalysis XXIVolume 11 From Catalysis to Lewis Base Catalysis with Highlights from 1806 to 1970 1Edwin Vedejs1.1 Introduction 11.2 Catalysis 11.3 Progress with Catalysis in Organic Chemistry 31.4 Ostwald’s Redefinition of Catalysis 51.5 The First Example of Lewis Base Catalysis 71.6 The Road to Mechanistic Comprehension; Multistage Catalysis by Lewis Base 91.7 An Uneven Path to a Unifying Concept 121.8 Amine Catalysis 171.9 Summary 26Section I Principles 312 Principles, Definitions, Terminology, and Orbital Analysis of Lewis Base–Lewis Acid Interactions Leading to Catalysis 33Scott E. Denmark and Gregory L. Beutner2.1 Introduction 332.2 Lewis Definitions of Valence and the Chemical Bond 342.3 Extensions, Expansions of, and Objections to the Lewis Definitions 352.4 Interpretation of the Lewis Definitions in the Idiom of Molecular Orbital Theory and Quantum Mechanics 382.5 Defining Lewis Base Catalysis 402.6 Theoretical Analysis of the Geometrical and Electronic Consequences of Lewis Acid–Lewis Base Interactions 442.7 Summary 513 Thermodynamic Treatments of Lewis Basicity 55Jean-François Gal3.1 Introduction 553.2 Basic Thermodynamics for the Study of Lewis Acid–Base Interactions 563.3 Scales of Lewis Affinity and Basicity 583.4 Lewis Acidity and Lewis Basicity: Thermodynamic Scales 623.5 Quantum Chemical Tools 743.6 Conclusion and Overview 753.7 Summary 76List of Abbreviations 774 Quantitative Treatments of Nucleophilicity and Carbon Lewis Basicity 85Sami Lakhdar4.1 Introduction 854.2 Nucleophilicity 854.3 Lewis Basicity 914.4 Nucleofugality 934.5 Selected Applications 954.6 Conclusion 1134.7 Summary 113Section II Mechanism and Lewis Base Catalysis: Nucleophilicity Is Only Part of the Story 1195 Anhydride Activation by 4-Dialkylaminopyridines and Analogs 121Raman Tandon and Hendrik Zipse5.1 Historical Background 1215.2 Mechanistic Considerations 1215.3 Catalyst Structure and Variation 1245.4 The Influence of Reaction Conditions 1305.5 The Influence of Acyl Donors 1325.6 The Influence of Substrate Structure 1365.7 Summary 1416 Mechanistic Understanding of Proline Analogs and Related Protic Lewis Bases 145Alan Armstrong and Paul Dingwall6.1 Proline Catalysis: Overview 1456.2 Mechanism of the Proline-Catalyzed Aldol Reaction 1476.3 Mechanism of the Proline-Catalyzed α-Amination and α-Aminoxylation Reactions 1616.4 The Proline-Mediated Conjugate Addition Reaction 1706.5 Modified Proline Derivatives 1756.6 Concluding Remarks 1867 Mechanistic Options for the Morita–Baylis–Hillman Reaction 191Marilia S. Santos, José Tiago M. Correia, Ana Paula L. Batista, Manoel T. Rodrigues Jr., Ataualpa A. C. Braga, Marcos N. Eberlin, and Fernando Coelho7.1 The Morita–Baylis–Hillman Reaction: An Overview 1917.2 Kinetic Studies Applied to aza-Morita–Baylis–Hillman Reaction 1957.3 Theoretical Calculations Applied to MBH Reaction 2087.4 Mass Spectrometry Aid the Understanding of the Morita–Baylis–Hillman Reaction 2177.5 Classical and Nonclassical Methods for Mechanistic Studies Associated with the Morita–Baylis–Hillman Reaction: Which Is the Correct Pathway of This Reaction? 2268 Mechanism of C-Si Bond Cleavage Using Lewis Bases 233Hans J. Reich8.1 Introduction 2338.2 Mechanistic Issues 2358.3 Alkylation 2478.4 Benzylation 2538.5 Allylation 2558.6 Allenylation/Propargylation 2608.7 Alkynylation 2618.8 Arylation 2628.9 Vinylation 2638.10 Cyanation 2648.11 Summary 2759 Bifunctional Lewis Base Catalysis with Dual Activation of X3Si-Nu and C=)O 2819.1 Addition of Allyltrichlorosilanes to Aldehydes 2819.2 Aldol Additions of Trichlorosilyl Enol Ethers Derived from Ketones, Aldehydes, and Esters 29310 Bifunctional Lewis Base Catalysis with Dual Activation of R–M and C=O 33910.1 Introduction 33910.2 Activation of C–Zn and Related C–Mg by a Simple Lewis Base 34010.3 Lewis Base-Activated C–Zn + C10.4 Role of Dimeric Organozinc Species 34510.5 Scope of Carbonyl Substrates in Catalytic Asymmetric Organozinc Addition Reaction 35010.6 Anionic Lewis Base Activation in Mg(II) and Zn(II) Ate Complexes 37210.7 Summary 38211 The Corey–Bakshi–Shibata Reduction: Mechanistic and Synthetic Considerations – Bifunctional Lewis Base Catalysis with Dual Activation 387Christopher J. Helal and Matthew P. Meyer11.1 Introduction 38711.2 The Catalytic Cycle 38911.3 Mechanism 39311.4 Applications of the CBS Reduction in Organic Synthesis 416Volume 2Section III Applications: Lewis Base Catalysis Involving an Activation Step 45712 Chiral Lewis Base Activation of Acyl and Related Donors in Enantioselective Transformations 459James I. Murray, Zsofia Heckenast, and Alan C. Spivey13 Catalytic Generation of Ammonium Enolates and Related Tertiary Amine-Derived Intermediates: Applications, Mechanism, and Stereochemical Models 527Khoi N. Van, Louis C. Morrill, Andrew D. Smith, and Daniel Romo14 Morita–Baylis–Hillman, Vinylogous Morita–Baylis–Hillman, and Rauhut–Currier Reactions 655Allison M. Wensley, Nolan T. McDougal, and Scott E. Schaus15 Beyond the Morita–Baylis–Hilman Reaction 715Yi Chiao Fan and Ohyun Kwon16 Iminium Catalysis 805Aurélie Claraz, Juha H. Siitonen, and Petri M. Pihko17 Enamine-Mediated Catalysis 857John J. Murphy, Mattia Silvi, and Paolo MelchiorreVolume 3Section IVa Applications: Enhanced Nucleophilicity by Lewis Base Activation 90318 Si-C-X and Si-C-EWG as Carbanion Equivalents under Lewis Base Activation 905Ping Fang, Chang-Hua Ding, and Xue-Long Hou19 Activation of B-B and B-Si Bonds and Synthesis of Organoboron and Organosilicon Compounds through Lewis Base-Catalyzed Transformations 967Amir H. Hoveyda, Hao Wu, Suttipol Radomkit, Jeannette M. Garcia, Fredrik Haeffner, and Kang-sang LeeSection IVb Applications: Enhanced Electrophilicity and Dual Activation by Lewis Base Catalysis 101120 Lewis Base-Catalyzed Reactions of SiX3-Based Reagents with C21 Lewis Base-Catalyzed, Lewis Acid-Mediated Reactions 1039Sergio Rossi and Scott E. Denmark22 Lewis Bases as Catalysts in the Reduction of Imines and Ketones with Silanes 1077Pavel Kočovský and Andrei V. Malkov23 Reactions of Epoxides 1113Tyler W. Wilson and Scott E. DenmarkSection V Lewis Base-Catalyzed Generation of Electrophilic Intermediates 115324 Lewis Base Catalysis: A Platform for Enantioselective Addition to Alkenes Using Group 16 and 17 Lewis Acids 1155Dipannita Kalyani, David J.-P. Kornfilt, Matthew T. Burk, and Scott E. DenmarkSection VI Bifunctional (and Multifunctional) Catalysis 121325 Bifunctional and Synergistic Catalysis: Lewis Acid Catalysis and Lewis Base-Assisted Bond Polarization 1215Won-jin Chung and Scott E. Denmark26 Bifunctional Catalysis with Lewis Base and X-H Sites That Facilitate Proton Transfer or Hydrogen Bonding 1259Curren T. Mbofana and Scott J. MillerSection VII Carbenes: Lewis Base Catalysis Triggers Multiple Activation Pathways 128927 Catalysis with Stable Carbenes 1291Darrin M. Flanigan, Nicholas A. White, Kevin M. Oberg, and Tomislav RovisSummation 1351Index 1355