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Comprehensive Enantioselective Organocatalysis: Catalysts, Reactions, and Applications, 3 Volume Set

Peter I. Dalko (Editor)
ISBN: 978-3-527-33236-6
1638 pages
December 2013
Comprehensive Enantioselective Organocatalysis: Catalysts, Reactions, and Applications, 3 Volume Set (3527332367) cover image
A much-needed overview reflecting the developments over the past five years, this is the most comprehensive handbook on organocatalysis. As such, all relevant catalyst systems are discussed in detail, as well as key strategies, reaction types, and important applications in total synthesis. The first two volumes cover catalyst structures and fundamental activation types. These chapters allow readers to familiarize themselves with the relatively complex interactions that make organocatalytic reactions selective; to gain an insight into the most efficient catalyst types; and to understand the importance of physical parameters that influence reactivity and selectivity. Volume three is structured around reaction types, i.e. nucleophile additions to C=X and C=C bonds; Friedel-Crafts reactions, organocatalytic sigmatropic reactions, regioselective reactions and desymmetrization strategies, ring-forming reactions, multicomponent (domino) reactions, multicatalyst systems and the application of organocatalytic reactions in multistep synthesis are discussed. An appendix recollecting catalyst structures with the adequate cross-references to the corresponding chapters rounds off the book.
With its contributions written by pioneers of the organocatalysis field, this book provides non-specialists with an introduction to the topic as well as serving as a valuable source for researchers in academia and industry searching for an up-to-date and comprehensive overview of this promising area of synthetic organic chemistry.
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Foreword XXVII

Preface XXIX

List of Contributors XXXI

Abbreviations XLI

Volume 1: Privileged Catalysts

Part I Amino Acid-Derived Catalysts 1

1 Proline-Related Secondary Amine Catalysts and Applications 3
Hiyoshizo Kotsuki and Niiha Sasakura

1.1 Introduction 3

1.2 Prolinamide and Related Catalysts 3

1.3 Prolinamine and Related Catalysts 8

1.4 Proline Tetrazole and Related Catalysts 10

1.5 Prolinamine Sulfonamide and Related Catalysts 13

1.6 Prolinamine Thiourea and Related Catalysts 15

1.7 Miscellaneous 16

1.8 Conclusions 21

Acknowledgments 21

References 21

2 TMS-Prolinol Catalyst in Organocatalysis 33
Hao Jiang, Łukasz Albrecht, Gustav Dickmeiss, Kim L. Jensen, and Karl Anker Jorgensen

2.1 Introduction 33

2.2 Enamine Activation 34

2.3 Iminium-Ion Activation 37

2.4 Cascade Reactions 41

2.5 Dienamine Activation 42

2.6 Trienamine Activation 46

2.7 Summary and Conclusions 48

References 48

3 Non-Proline Amino Acid Catalysts 51
Li-Wen Xu and Yixin Lu

3.1 Introduction 51

3.2 Primary Amino Acids in Amino Catalysis 52

3.3 Primary Amino Acid-Derived Organic Catalysts 53

3.4 Applications of Non-Proline Primary Amino Acid Catalysts 56

3.5 Conclusions 65

Acknowledgments 66

References 66

4 Chiral Imidazolidinone (MacMillan’s) Catalyst 69
Rainer Mahrwald

4.1 Introduction 69

4.2 Enamine Catalysis 69

4.3 Iminium Catalysis 81

4.4 Cascade Reaction – Merging Iminium and Enamine Catalysis 86

References 91

5 Oligopeptides as Modular Organocatalytic Scaffolds 97
Roberto Fanelli and Umberto Piarulli

5.1 Introduction 97

5.2 C–C Bond Forming Reactions 98

5.3 Asymmetric Acylations 108

5.4 Asymmetric Phosphorylations 110

5.5 Enantioselective Oxidations 111

5.6 Hydrolytic Reactions 114

5.7 Summary and Conclusions 114

References 114

Part II Non-Amino Acid-Derived Catalysts 117

6 Cinchonas and Cupreidines 119
Steen Ingemann and Henk Hiemstra

6.1 Introduction 119

6.2 Cinchona Alkaloid Derivatives 120

6.3 Natural Cinchona Alkaloids, Cupreine, and Cupreidine 121

6.4 Cinchona Alkaloids with an Ether or Ester Group at C9 127

6.5 Cinchona Alkaloid Derivatives with a Sulfonamide, Urea, Thiourea, Squaramide, or Guanidine Function 134

6.6 Cinchona Alkaloids with a Primary Amine Group at C9 145

6.7 Cinchona Alkaloids in Phase-Transfer Catalysis 149

6.8 Ether Bridged Dimers 151

6.9 Some Novel Cinchona Alkaloid Derivatives 153

6.10 Prospects 154

References 155

7 Chiral C2 Catalysts 161
Daisuke Uraguchi, Kohsuke Ohmatsu, and Takashi Ooi

7.1 Introduction 161

7.2 Chiral Lewis Base Catalysts 161

7.3 Phosphines 172

7.4 Chiral C2-Symmetric Secondary and Primary Amines 174

7.5 Chiral C2-Symmetric Brønsted Bases: Guanidines 177

7.6 Chiral C2-Symmetric Brønsted Acids 181

7.7 Chiral C2-Symmetric Bis-Thioureas 188

7.8 Chiral C2-Symmetric Aminophosphonium Ions 189

7.9 Summary and Conclusions 190

References 190

8 Planar Chiral Catalysts 195
Olivier R.P. David

8.1 Introduction 195

8.2 Lewis/Brønsted Bases 198

8.3 Lewis/Brønsted Acids 211

8.4 Redox Reactions 213

8.5 Summary and Conclusions 214

References 215

9 Dynamic Approaches towards Catalyst Discovery 221
Patrizia Galzerano, Giulio Gasparini, Marta Dal Molin, and Leonard J. Prins

9.1 Introduction 221

9.2 Self-Assembly 222

9.3 Self-Selected Catalysts 232

9.4 Conclusions 236

Acknowledgments 236

References 236

Appendix A1

Volume 2: Activations

Part I Asymmetric Catalysis with Non-Covalent Interactions 239

10 Brønsted Acids 241
Yunus E. Turkmen, Ye Zhu, and Viresh H. Rawal

10.1 Introduction 241

10.2 Chiral Alcohol Catalysts 245

10.3 Chiral Squaramides as Hydrogen-Bond Donor Catalysts 252

10.4 Guanidines/Guanidiniums 269

10.5 Miscellaneous Brønsted Acids 275

10.6 Addendum 282

References 282

11 Brønsted Acids: Chiral Phosphoric Acid Catalysts in Asymmetric Synthesis 289
Keiji Mori and Takahiko Akiyama

11.1 Introduction 289

11.2 Reaction with Imines 291

11.3 Friedel–Crafts Reaction 304

11.4 Intramolecular Aldol Reaction 309

11.5 Ring Opening of meso-Aziridines 311

11.6 Future Prospects 312

References 312

12 Brønsted Acids: Chiral (Thio)urea Derivatives 315
Gergely Jakab and Peter R. Schreiner

12.1 Introduction 315

12.2 Important Chiral (Thio)urea Organocatalysts 318

12.3 Summary 336

References 336

13 Brønsted Bases 343
Amal Ting and Scott E. Schaus

13.1 Introduction 343

13.2 Cinchona Alkaloids 344

13.3 Brønsted Base-Derived Thiourea Catalysts 352

13.4 Chiral Guanidine Catalysts 356

13.5 Conclusion 361

References 361

14 Chiral Onium Salts (Phase-Transfer Reactions) 365
Seiji Shirakawa and Keiji Maruoka

14.1 Introduction 365

14.2 Phase-Transfer Catalysis 366

14.3 Onium Fluorides 372

14.4 Onium Phenoxides and Related Compounds 374

14.5 Conclusions 377

References 377

15 Lewis Bases 381
Pavel Kočovsky and Andrei V. Malkov

15.1 Introduction 381

15.2 Allylation Reactions 382

15.3 Propargylation, Allenylation, and Addition of Acetylenes 395

15.4 Aldol-Type Reactions 396

15.5 Cyanation and Isonitrile Addition 404

15.6 Reduction Reactions 408

15.7 Epoxide Opening 417

15.8 Conclusion and Outlook 421

References 421

16 Lewis Acids 431
Tatjana Heckel and Rene Wilhelm

16.1 Introduction 431

16.2 Silyl Cation Based Catalysts 433

16.3 Hypervalent Silicon Based Catalysts 438

16.4 Phosphonium Cation Based Catalysts 444

16.5 Carbocation Based Catalysts 448

16.6 Ionic Liquids 455

16.7 Miscellaneous Catalysts 458

16.8 Conclusion 459

References 459

Part II Asymmetric Catalysis with Covalent Interactions 463

17 Rationalizing Reactivity and Selectivity in Aminocatalytic Reactions 465
Raghavan B. Sunoj

17.1 Introduction 465

17.2 Secondary Amine Catalysis 466

17.3 Stereoselectivity in Proline-Catalyzed Reactions 472

17.4 Mechanism and Stereoselectivity in Organocatalytic Cascade Reactions 482

17.5 Rational Design of Catalysts 486

17.6 Summary and Conclusions 491

Acknowledgments 492

References 492

18 Carbene Catalysts 495
Karen Thai, Eduardo Sanchez-Larios, and Michel Gravel

18.1 Introduction 495

18.2 Reactions of Acyl Anion Equivalents 497

18.3 Extended Umpolung 506

18.4 Umpolung of Activated Olefi ns 514

18.5 Nucleophilic Catalysis 515

18.6 Conclusion 518

References 518

19 Oxides and Epoxides 523
Harry J. Milner and Alan Armstrong

19.1 Alkene Epoxidation 523

19.2 Hypervalent Iodine-Catalyzed Oxidations 537

19.3 Oxidation of Thioethers and Disulfi des 539

19.4 Resolution of Alcohols by Oxidation 540

References 542

20 Ylides 547
Saihu Liao, Peng Wang, and Yong Tang

20.1 Introduction 547

20.2 Enantioselective Sulfur Ylide Catalysis 548

20.3 Enantioselective Phosphorus and Arsenic Ylide Catalysis 566

20.4 Enantioselective Nitrogen Ylide Catalysis 570

20.5 Enantioselective Selenium and Tellurium Ylide Catalysis 573

20.6 Summary and Conclusions 574

References 575

Part III Tuning Catalyst Activity and Selectivity by the Reaction Medium and Conditions 579

21 “Non-Classical” Activation of Organocatalytic Reactions (Pressure, Microwave Irradiation.) 581
Piotr Kwiatkowski, Krzysztof Dudziński, and Dawid Łyżwa

21.1 Introduction 581

21.2 Asymmetric Organocatalysis under High-Pressure Conditions 581

21.3 Asymmetric Organocatalysis under Microwave Irradiation – Thermal Effect 593

21.4 Asymmetric Organocatalysis under Ultrasound Irradiation 601

21.5 Asymmetric Organocatalysis under Ball Milling Conditions 605

21.6 Summary and Conclusions 612

References 613

22 Ionic Liquid Organocatalysts 617
Dmitry E. Siyutkin, Alexander S. Kucherenko, and Sergei G. Zlotin

22.1 Introduction 617

22.2 Ionic Liquids as Recyclable Solvents for Asymmetric Organocatalytic Reactions 618

22.3 “Non-Solvent” Applications of Ionic Liquids and Their Congeners in Asymmetric Organocatalysis 625

22.4 Conclusion 646

References 647

23 Polymer and Mesoporous Material Supported Organocatalysts 651
Tor Erik Kristensen and Tore Hansen

23.1 Introduction 651

23.2 Polymer-Supported Organocatalysts 652

23.3 Mesoporous-Supported Organocatalysts 663

23.4 Conclusions and Outlook 668

References 668

24 Water in Organocatalytic Reactions 673
Francesco Giacalone and Michelangelo Gruttadauria

24.1 Introduction 673

24.2 Aldol Reactions 678

24.3 Michael Reactions 696

24.4 Mannich Reaction 705

24.5 Diels–Alder Reaction 707

24.6 Miscellaneous Examples 710

References 713

Volume 3: Reactions and Applications

Part I Alpha-Alkylation and Heteroatom Functionalization 719

25 SN2-Type Alpha-Alkylation and Allylation Reactions 721
Christine Tran and Peter I. Dalko

25.1 SN2-Type Alkylation under Homogenous Conditions 721

25.2 Domino Reactions Including SN2-Type Alkylations 722

25.3 Intermolecular SN2′ Alkylations under Homogenous Conditions 726

25.4 Summary 727

References 727

26 Alpha-Alkylation by SN1-Type Reactions 729
Andrea Gualandi, Diego Petruzziello, Enrico Emer, and Pier Giorgio Cozzi

26.1 Introduction 729

26.2 SN1-Type Nucleophilic Reaction by Generation of Carbocations 730

26.3 Organocatalytic Stereoselective SN1-Type Reactions with Enamine Catalysis 733

26.4 Asymmetric SN1-Type α-Alkylation of Ketones 737

26.5 Combination of Enamine Catalysis and Lewis Acids in SN1-Type Reactions 738

26.6 Organocatalytic SN1-Type Reactions with Brønsted Acids 741

26.7 SN1-Type Reaction Promoted by Chiral Thioureas 747

26.8 SN1-Type Organocatalytic Reaction of Iminium, Oxonium, and Aziridinium Intermediates 749

26.9 Conclusions and Perspectives 751

References 751

27 Alpha-Heteroatom Functionalization of Carbonyl Compounds 757
Gabriela Guillena

27.1 Introduction 757

27.2 Enantioselective α-Pnictogenation of Carbonyl Compounds 758

27.3 Enantioselective α-Chalcogenation 770

27.4 Enantioselective α-Halogenation of Carbonyl Compounds 779

27.5 Summary and Conclusions 783

References 783

Part II Nucleophile Addition to C=X Bonds 791

28 Aldol and Mannich-Type Reactions 793
Nobuyuki Mase and Carlos F. Barbas III

28.1 Introduction 793

28.2 Enamine Catalysis 795

28.3 Brønsted Acid Catalysis Including Hydrogen-Bond Catalysis 810

28.4 Brønsted Base Catalysis Including Bifunctional Catalysis 817

28.5 Phase-Transfer Catalysis 824

28.6 N-Heterocyclic Carbene (NHC) Catalysis 829

28.7 Supported Organocatalysis 831

28.8 Summary and Conclusions 835

References 835

29 Additions of Nitroalkyls and Sulfones to C=X 841
Aitor Landa, Rosa Lopez, Mikel Oiarbide, and Claudio Palomo

29.1 Organocatalytic Addition of Nitroalkanes to C=O (The Henry Reaction) 841

29.2 Addition of Nitroalkanes to C=NR (The Aza-Henry or Nitro-Mannich Reaction) 851

29.3 Organocatalytic Addition of Sulfones to C=X 864

29.4 Summary and Outlook 868

References 868

30 Hydrocyanation and Strecker Reactions 873
Carsten Kramer and Stefan Brase

30.1 Introduction 873

30.2 Amino-Acid Containing Catalysts for Carbonyl Hydrocyanation 873

30.3 Thiourea Catalysts for Carbonyl Hydrocyanation 875

30.4 C2-Symmetrical Guanidines and N,N′-Dioxides 876

30.5 Diketopiperazines as Catalysts for the Strecker Reaction 877

30.6 (Thio)urea Catalysts for the Strecker Reaction 878

30.7 Guanidines as Catalysts for the Strecker Reaction 886

30.8 N,N′-Dioxides and Bis-Formamides as Catalysts for the Strecker Reaction 886

30.9 Chiral Quaternary Ammonium Salts as Catalysts for the Strecker Reaction 890

30.10 BINOL-Phosphates as Catalysts for the Strecker Reaction 893

30.11 Other Catalysts for the Strecker Reaction 895

References 896

31 The Morita–Baylis–Hillman (MBH) and Hetero-MBH Reactions 899
Yin Wei and Min Shi

31.1 Introduction 899

31.2 Recent Mechanistic Insights into the MBH/aza-MBH Reaction and Its Asymmetric Version 900

31.3 Recent Developments of Essential Components 910

31.4 Recent Developments of Asymmetric MBH/aza-MBH Reactions 914

31.5 Conclusions 937

References 938

32 Reduction of C=O and C=N 941
Guilong Li and Jon C. Antilla

32.1 Introduction 941

32.2 Hantzsch Ester as the Hydride Source 941

32.3 Trichlorosilane as the Reducing Reagent 955

32.4 Other Hydrogen Sources 964

32.5 Summary and Conclusions 971

References 971

Part III Nucleophile Addition to C=C Bonds 975

33 Addition to α,β-Unsaturated Aldehydes and Ketones 977
Ramon Rios and Xavier Companyo

33.1 Introduction 977

33.2 Nucleophilic Addition to Enals and Ketones 979

33.3 Conclusion 1008

References 1008

34 Addition to Nitroolefi ns and Vinyl Sulfones 1013
Christele Roux and Cyril Bressy

34.1 Introduction 1013

34.2 Addition to Nitroolefi ns 1013

34.3 Addition to Vinyl Sulfones 1032

34.4 Addition to Vinyl Selenones 1037

34.5 Summary and Conclusions 1040

Acknowledgments 1040

References 1040

35 Organocatalyzed Asymmetric Arylation and Heteroarylation Reactions 1043
Renata Marcia de Figueiredo and Jean-Marc Campagne

35.1 Introduction 1043

35.2 Representative Classes of Electrophiles 1046

35.3 Friedel–Crafts in Organocascade Transformations 1053

35.4 Application in Biologically Interesting and Natural Product Syntheses 1057

35.5 Miscellaneous 1061

35.6 Conclusion 1062

References 1063

Part IV Ring-Forming Reactions 1067

36 Intramolecular Reactions 1069
You-Cai Xiao and Ying-Chun Chen

36.1 Introduction 1069

36.2 Intramolecular Ring-Forming Reactions via Covalent Catalysis 1070

36.3 Intramolecular Ring-Forming Reactions by Non-Covalent Catalysis 1081

36.4 Conclusion 1087

References 1087

37 Formation of 3-, 4- and 5-Membered Cycles by Intermolecular Reactions 1091
Helene Pellissier

37.1 Introduction 1091

37.2 Organocatalytic Asymmetric Synthesis of Five-Membered Cycles 1092

37.3 Organocatalytic Asymmetric Synthesis of Four-Membered Cycles 1112

37.4 Organocatalytic Asymmetric Synthesis of Three-Membered Cycles 1115

37.5 Conclusion 1123

References 1124

38 Diels-Alder and Hetero-Diels–Alder Reactions 1131
Haifeng Du and Kuiling Ding

38.1 Introduction 1131

38.2 Organocatalytic Diels–Alder Reaction 1132

38.3 Organocatalysis of Oxa-Hetero-Diels–Alder Reaction 1147

38.4 Organocatalysis of Aza-Hetero-Diels–Alder Reaction 1154

38.5 Conclusion 1159

References 1160

Part V Increasing Complexity 1163

39 Organocatalytic Radical and Electron Transfer Reactions 1165
Thibault Gallavardin and Peter I. Dalko

39.1 Introduction 1165

39.2 Chemically Induced Oxidative Electron-Transfer Reactions 1166

39.3 Photoredox Catalysis 1180

39.4 Photochemical Asymmetric Synthesis 1186

39.5 Conclusion 1188

References 1189

40 Organocatalytic Sigmatropic Reactions 1191
Guillem Valero and Albert Moyano

40.1 Introduction 1191

40.2 Steglich and Related Rearrangements 1192

40.3 1,3-Sigmatropic Rearrangements 1203

40.4 1,4-Sigmatropic Rearrangements 1207

40.5 2,3-Sigmatropic Rearrangements 1208

40.6 3,3-Sigmatropic Rearrangements 1209

40.7 Aza-Petasis–Ferrier Rearrangement 1215

40.8 Pinacol and Related Rearrangements 1216

Acknowledgments 1220

References 1220

41 Regio- and Position Selective Reactions and Desymmetrizations 1225
Alan C. Spivey and Stellios Arseniyadis

41.1 Introduction 1225

41.2 Kinetic Resolution of Alcohols 1225

41.3 Kinetic Resolution of Amines 1263

41.4 Concluding Remarks 1278

References 1279

42 Three or More Components Reactions (Single Catalyst Systems) 1285
Rene Tannert, Antonio Moran, and Paolo Melchiorre

42.1 General Introduction 1285

42.2 Covalent Modes of Catalysis – Developing MCRs by Asymmetric Aminocatalysis 1287

42.3 Non-Covalent Modes of Catalysis 1309

42.4 Merging Covalent and Non-Covalent Activation Modes 1325

42.5 Summary and Outlook 1326

Acknowledgments 1327

References 1327

43 Multi-Catalyst Systems 1333
Liwen Xu, Huameng Yang, and Zhihui Shao

43.1 Introduction 1333

43.2 Combinational Use of Dual Brønsted Acids 1334

43.3 Combinational Use of Chiral Brønsted Acid and Chiral or Achiral Lewis Base 1335

43.4 Carbene-Based Dual Organocatalysis 1338

43.5 Amino Catalyst-Based Cooperative Catalysis with Multifarious Co-Catalysts 1343

43.6 Conclusions 1354

Acknowledgments 1355

References 1355

44 Organocatalysis in Total Synthesis 1359
Eugenia Marques-Lopez and Raquel P. Herrera

44.1 Introduction 1359

44.2 Aminocatalysis in Natural Product Synthesis 1359

44.3 Hydrogen Bond Catalysis in Total Synthesis 1365

44.4 Cinchona Alkaloids in Total Synthesis 1370

44.5 Phase-Transfer Catalysis in Target Molecule Synthesis 1371

44.6 Industrial Applications of Organocatalysis 1373

44.7 Conclusions 1376

References 1377

Index 1385

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Peter I. Dalko studied chemistry at the Budapest Technical University (Hungary) and graduated from Paris XI University (France) under the supervision of Stephan D. Géro. After undertaking postdoctoral research with Sir Derek H. Barton at Texas A&M University (USA) and Yoshito Kishi at Harvard University he joined Janine Cossy's research group at the ESPCI in Paris. He is now a Research Director at the French Scientific Research Council (CNRS) at the Medical Faculty of Paris Descartes University. His research is focused on total synthesis of structurally complex natural products, development of organocatalytic reactions for synthesis and developing micro- and nanoscale technologies for biomedical researches.
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