Lewis Base Catalysis in Organic Synthesis E-Book

• Herausgeber: Wiley-VCH Verlag GmbH & Co. KGaA
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 2367

Veröffentlichungsjahr: 2016

Beschreibung

This three-volume set represents the first comprehensive coverage of the rapidly expanding field of Lewis base catalysis that has attracted enormous attention in recent years. Lewis base catalysis is a conceptually novel paradigm that encompasses an extremely wide variety of preparatively useful transformations and is particularly effective for enantioselectively constructing new stereogenic centers. As electron-pair donors, Lewis bases can influence the rate and stereochemical course of myriad synthetic organic reactions. The book presents the conceptual/mechanistic principles that underlie Lewis base catalysis, and then builds upon that foundation with a thorough presentation of many different reaction types. And last but not least, the editors, Prof. Edwin Vedejs and Prof. Scott E. Denmark, are without doubt the leaders in this emerging field and have compiled high quality contributions from an impressive collection of international experts.

Leseprobe

CONTENTS

Cover

Title Page

Copyright

Preface for Volumes 1–3

Introduction: Definitions of Catalysis

Volume 1

Chapter 1: From Catalysis to Lewis Base Catalysis with Highlights from 1806 to 1970

1.1 Introduction

1.2 Catalysis

1.3 Progress with Catalysis in Organic Chemistry

1.4 Ostwald's Redefinition of Catalysis

1.5 The First Example of Lewis Base Catalysis

1.6 The Road to Mechanistic Comprehension; Multistage Catalysis by Lewis Base

1.7 An Uneven Path to a Unifying Concept

1.8 Amine Catalysis

1.9 Summary

Acknowledgment

References

Section I: Principles

Chapter 2: Principles, Definitions, Terminology, and Orbital Analysis of Lewis Base–Lewis Acid Interactions Leading to Catalysis

2.1 Introduction

2.2 Lewis Definitions of Valence and the Chemical Bond

2.3 Extensions, Expansions of, and Objections to the Lewis Definitions

2.4 Interpretation of the Lewis Definitions in the Idiom of Molecular Orbital Theory and Quantum Mechanics

2.5 Defining Lewis Base Catalysis [17]10

2.6 Theoretical Analysis of the Geometrical and Electronic Consequences of Lewis Acid–Lewis Base Interactions

2.7 Summary

References

Chapter 3: Thermodynamic Treatments of Lewis Basicity

3.1 Introduction

3.2 Basic Thermodynamics for the Study of Lewis Acid–Base Interactions

3.3 Scales of Lewis Affinity and Basicity

3.4 Lewis Acidity and Lewis Basicity: Thermodynamic Scales

3.5 Quantum Chemical Tools

3.6 Conclusion and Overview

3.7 Summary

List of Abbreviations

Acknowledgments

References

Chapter 4: Quantitative Treatments of Nucleophilicity and Carbon Lewis Basicity

4.1 Introduction

4.2 Nucleophilicity

4.3 Lewis Basicity

4.4 Nucleofugality

4.5 Selected Applications

4.6 Conclusion

4.7 Summary

List of Abbreviations

Acknowledgments

References

Section II: Mechanism and Lewis Base Catalysis: Nucleophilicity Is Only Part of the Story

Chapter 5: Anhydride Activation by 4-Dialkylaminopyridines and Analogs (n → π*)

5.1 Historical Background

5.2 Mechanistic Considerations

5.3 Catalyst Structure and Variation

5.4 The Influence of Reaction Conditions

5.5 The Influence of Acyl Donors

5.6 The Influence of Substrate Structure

5.7 Summary

List of Abbreviations

References

Chapter 6: Mechanistic Understanding of Proline Analogs and Related Protic Lewis Bases (n → π*)

6.1 Proline Catalysis: Overview

6.2 Mechanism of the Proline-Catalyzed Aldol Reaction

6.3 Mechanism of the Proline-Catalyzed α-Amination and α-Aminoxylation Reactions

6.4 The Proline-Mediated Conjugate Addition Reaction

6.5 Modified Proline Derivatives

6.6 Concluding Remarks

List of Abbreviations

References

Chapter 7: Mechanistic Options for the Morita–Baylis–Hillman Reaction (n → π*)

7.1 The Morita–Baylis–Hillman Reaction: An Overview

7.2 Kinetic Studies Applied to aza-Morita–Baylis–Hillman Reaction

7.3 Theoretical Calculations Applied to MBH Reaction

7.4 Mass Spectrometry Aids the Understanding of the Morita–Baylis–Hillman Reaction

7.5 Classical and Nonclassical Methods for Mechanistic Studies Associated with the Morita–Baylis–Hillman Reaction: Which Is the Correct Pathway of This Reaction?

Acknowledgments

List of Abbreviations

References

Chapter 8: Mechanism of C—Si Bond Cleavage Using Lewis Bases (n → σ*)

8.1 Introduction

8.2 Mechanistic Issues

8.3 Alkylation

8.4 Benzylation

8.5 Allylation

8.6 Allenylation/Propargylation

8.7 Alkynylation

8.8 Arylation

8.9 Vinylation

8.10 Cyanation

8.11 Summary

List of Abbreviations

References

Chapter 9: Bifunctional Lewis Base Catalysis with Dual Activation of X3Si—Nu and C=O (n → σ*)

9.1 Addition of Allyltrichlorosilanes to Aldehydes

9.2 Aldol Additions of Trichlorosilyl Enol Ethers Derived from Ketones, Aldehydes, and Esters

List of Abbreviations

References

Chapter 10: Bifunctional Lewis Base Catalysis with Dual Activation of R–M and C=O (n → σ*)

10.1 Introduction

10.2 Activation of C–Zn and Related C–Mg by a Simple Lewis Base

10.3 Lewis Base-Activated C–Zn + C=O Reactions

10.4 Role of Dimeric Organozinc Species

10.5 Scope of Carbonyl Substrates in Catalytic Asymmetric Organozinc Addition Reaction

10.6 Anionic Lewis Base Activation in Mg(II) and Zn(II) Ate Complexes

10.7 Summary

List of Abbreviations

References

Chapter 11: The Corey–Bakshi–Shibata Reduction: Mechanistic and Synthetic Considerations – Bifunctional Lewis Base Catalysis with Dual Activation

11.1 Introduction

11.2 The Catalytic Cycle

11.3 Mechanism

11.4 Applications of the CBS Reduction in Organic Synthesis

References

Volume 2

Section III: Applications: Lewis Base Catalysis Involving an n → π* Activation Step

Chapter 12: Chiral Lewis Base Activation of Acyl and Related Donors in Enantioselective Transformations (n → π*)

12.1 Introduction

12.2 Phosphine Catalysts

12.3 Amine Catalysts

12.4 N-Heterocyclic Carbene (NHC) Catalysts

12.5 Alcohol Catalysts

12.6 Concluding Remarks

List of Abbreviations

References

Chapter 13: Catalytic Generation of Ammonium Enolates and Related Tertiary Amine-Derived Intermediates: Applications, Mechanism, and Stereochemical Models (n → π*)

13.1 C(1)- and C(2)-Ammonium Enolates

13.2 α,β-Unsaturated Acylammonium Salts

13.3 Ammonium Dienolates via Net [4 + 2] Cycloadditions

13.4 Summary

List of Abbreviations

Acknowledgments

References

Chapter 14: Morita–Baylis–Hillman, Vinylogous Morita–Baylis–Hillman, and Rauhut–Currier Reactions

14.1 Introduction

14.2 Enantioselective Morita–Baylis–Hillman Reactions

14.3 The Vinylogous Morita–Baylis–Hillman Reaction

14.4 The Rauhut–Currier Reaction

14.5 Summary

List of Abbreviations

References

Chapter 15: Beyond the Morita–Baylis–Hillman Reaction (n → π*)

15.1 Introduction

15.2 Phosphine-Catalyzed Reactions of Activated Alkenes/Allenes/Alkynes

15.3 Phosphine-Catalyzed Generation of Brønsted Base: Michael Addition

15.4 Phosphine-Catalyzed Umpolung Additions

15.5 Brønsted Base-Assisted Phosphine Catalysis

15.6 Miscellaneous Phosphine-Catalyzed Processes

15.7 Chiral Phosphine Catalysis

15.8 Application in Total Synthesis

15.9 Conclusion

List of Abbreviations

References

Chapter 16: Iminium Catalysis (n → π*)

16.1 Introduction

16.2 Structural and Mechanistic Aspects of Iminium Catalysis

16.3 Enantioselectivity: MacMillan Catalysts and Geometry Control

16.4 Expanding the Diversity of Catalysts

16.5 Beyond Five-Membered Rings

16.6 Conclusions

List of Abbreviations

References

Chapter 17: Enamine-Mediated Catalysis (n → π*)

17.1 Introduction

17.2 Mechanistic Considerations

17.3 Michael Additions

17.4 Aldol Reactions

17.5 Mannich Reactions

17.6 Reactions of Heteroatomic Electrophiles

17.7 α-Alkylation of Enamines

17.8 Cycloadditions

17.9 Selected Applications

17.10 Conclusions

List of Abbreviations

Acknowledgments

References

Volume 3

Section IVa: Applications: Enhanced Nucleophilicity by Lewis Base Activation (n → σ*, n → n*)

Chapter 18: Si—C—X and Si—C—EWG as Carbanion Equivalents under Lewis Base Activation (n → σ*)

18.1 Introduction

18.2 Lewis Base-Induced Generation of Carbanion Equivalents with Si—C—EWG

18.3 CF3SiMe3 and Related Reagents; Lewis Base-Induced Transfer of “CF3−”

18.4 Potentially Catalytic Cases of Si—C—X Activation by Lewis Base; X = O, N, S, SMe2(+), and Related Reagents

18.5 Carbanion Generation from Selected Sn—C—X and Sn—C—EWG Analogs

18.6 Conclusion

List of Abbreviations

References

Chapter 19: Activation of B—B and B—Si Bonds and Synthesis of Organoboron and Organosilicon Compounds through Lewis Base-Catalyzed Transformations (n → n*)

19.1 Introduction

19.2 Lewis Base Activation of B—B Bonds and Catalytic C—B Bond Forming Processes

19.3 Lewis Base Activation of B—Si Bonds and Catalytic Silyl or Boryl Additions

19.4 Mechanistic Aspects of NHC-Catalyzed Boryl and Silyl Conjugate Additions

19.5 Conclusions and Outlook

List of Abbreviations

Acknowledgments

References

Section IVb: Applications: Enhanced Electrophilicity and Dual Activation by Lewis Base Catalysis (n → σ*)

Chapter 20: Lewis Base-Catalyzed Reactions of SiX3-Based Reagents with C=O, C=N (n → σ*)

20.1 Introduction

20.2 Allylation of C=O Substrates: Diastereoselection and Mechanistic Aspects

20.3 Chiral Catalysts for Enantioselective Allylation

20.4 Functionalized Allyltrichlorosilanes and Synthetic Applications of Allylation

20.5 Allylation of C=N Substrates

20.6 Propargylation and Allenylation of Aldehydes, Imines, and Hydrazones

20.7 Conclusion and Outlook

List of Abbreviations

References

Chapter 21: Lewis Base-Catalyzed, Lewis Acid-Mediated Reactions (n → σ*)

21.1 Introduction

21.2 Allylation Reactions

21.3 Aldol Reactions

21.4 Double-Aldol Additions

21.5 Vinylogous Aldol Additions

21.6 Passerini Reactions

21.7 Outlook and Perspective

List of Abbreviations

References

Chapter 22: Lewis Bases as Catalysts in the Reduction of Imines and Ketones with Silanes (n → σ*)

22.1 Introduction: Activation of Silanes

22.2 Reductive Amination of Aldehydes and Ketones with Trichlorosilane

22.3 Enantioselective Reduction of Ketimines with Trichlorosilane

22.4 Enantioselective Reduction of Functionalized Ketimines with Trichlorosilane

22.5 Enantioselective Reduction of Ketimines with Trialkoxysilanes

22.6 Enantioselective Reduction of Ketones with Trichlorosilane

22.7 Selected Synthetic Applications of the Enantioselective Reduction of Imines with Trichlorosilane

22.8 Conclusion

List of Abbreviations

References

Chapter 23: Reactions of Epoxides (n → σ*)

23.1 Introduction

23.2 Opening of Epoxides Catalyzed by Achiral Lewis Bases

23.3 Lewis Base-Catalyzed, Enantioselective Epoxide Opening

23.4 Mechanistic Studies on Lewis Base-Catalyzed Epoxide Opening

23.5 Enantioselective Opening of Epoxides with Fluoride

23.6 Summary

List of Abbreviations

References

Section V: Lewis Base-Catalyzed Generation of Electrophilic Intermediates

Chapter 24: Lewis Base Catalysis: A Platform for Enantioselective Addition to Alkenes Using Group 16 and 17 Lewis Acids (n → σ*)

24.1 Introduction

24.2 Selenofunctionalization

24.3 Sulfenofunctionalization

24.4 Halofunctionalization

24.5 Summary

List of Abbreviations

References

Section VI: Bifunctional (and Multifunctional) Catalysis

Chapter 25: Bifunctional and Synergistic Catalysis: Lewis Acid Catalysis and Lewis Base-Assisted Bond Polarization (n → σ*)

25.1 Introduction

25.2 Bifunctional Catalysis

25.3 Synergistic Catalysis

25.4 Bifunctional/Synergistic Catalysis with Fluoride Activation

25.5 Conclusion

List of Abbreviations

References

Chapter 26: Bifunctional Catalysis with Lewis Base and X-H Sites That Facilitate Proton Transfer or Hydrogen Bonding (n → π*)

26.1 Introduction

26.2 Group Transfer Reactions

26.3 Addition Reactions to Electron-Deficient Alkenes

26.4 Allenoate Reactions

26.5 Summary

List of Abbreviations

References

Section VII: Carbenes: Lewis Base Catalysis Triggers Multiple Activation Pathways

Chapter 27: Catalysis with Stable Carbenes (n → π*)

27.1 Introduction

27.2 N-Heterocyclic Carbenes as Lewis Base Catalysts: Structural and Electronic Considerations

27.3 N-Heterocyclic Carbenes in Classical Lewis Base-Catalyzed Reactions

27.4 N-Heterocyclic Carbenes in Nonclassical Lewis Base-Catalyzed Reactions

27.5 Selected Examples of N-Heterocyclic Carbenes in Synthesis

27.6 Summary

List of Abbreviations

References

Summation

Index

End User License Agreement

List of Tables

Table 1.1

Table 2.1

Table 3.1

Table 3.2

Table 3.3

Table 3.4

Table 3.5

Table 4.1

Table 4.2

Table 4.3

Table 4.4

Table 4.5

Table 4.6

Table 5.1

Table 5.2

Table 5.3

Table 6.1

Table 9.1

Table 9.2

Table 9.3

Table 9.4

Table 9.5

Table 9.6

Table 9.7

Table 9.8

Table 9.9

Table 9.10

Table 9.11

Table 10.1

Table 10.2

Table 10.3

Table 10.4

Table 10.5

Table 10.6

Table 11.1

Table 11.2

Table 11.3

Table 11.4

Table 11.5

Table 11.6

Table 11.7

Table 11.8

Table 11.9

Table 11.10

Table 11.11

Table 11.12

Table 11.13

Table 11.14

Table 11.15

Table 11.16

Table 11.17

Table 11.18

Table 11.19

Table 11.20

Table 11.21

Table 11.22

Table 12.1

Table 12.2

Table 12.3

Table 12.4

Table 12.5

Table 12.6

Table 12.7

Table 12.8

Table 12.9

Table 12.10

Table 12.11

Table 12.12

Table 12.13

Table 13.1

Table 13.2

Table 14.1

Table 15.1

Table 15.2

Table 15.3

Table 15.4

Table 15.5

Table 15.6

Table 15.7

Table 15.8

Table 15.9

Table 15.10

Table 15.11

Table 15.12

Table 15.13

Table 15.14

Table 15.15

Table 15.16

Table 15.17

Table 15.18

Table 16.1

Table 16.2

Table 16.3

Table 16.4

Table 16.5

Table 16.6

Table 16.7

Table 16.8

Table 16.9

Table 16.10

Table 20.1

Table 20.2

Table 21.1

Table 21.2

Table 21.3

Table 21.4

Table 21.5

Table 21.6

Table 21.7

Table 21.8

Table 21.9

Table 21.10

Table 21.11

Table 21.12

Table 21.13

Table 21.14

Table 21.15

Table 22.1

Table 22.2

Table 22.3

Table 22.4

Table 22.5

Table 22.6

Table 22.7

Table 22.8

Table 22.9

Table 22.10

Table 22.11

Table 22.12

Table 22.13

Table 22.14

Table 23.1

Table 23.2

Table 23.3

Table 23.4

Table 23.5

Table 23.6

Table 24.1

Table 24.2

Table 24.3

Table 24.4

Table 24.5

Table 24.6

Table 24.7

Table 25.1

Table 26.1

Table 26.2

Table 26.3

List of Illustrations

Scheme 1

Scheme 2

Scheme 1.1

Scheme 1.2

Scheme 1.3

Scheme 1.4

Scheme 1.5

Scheme 1.6

Scheme 1.7

Scheme 1.8

Scheme 1.9

Scheme 2.1

Figure 2.1

Scheme 2.2

Scheme 2.3

Scheme 2.4

Scheme 2.5

Figure 2.2

Figure 2.3

Scheme 4.1

Figure 4.1

Figure 4.2

Figure 4.3

Scheme 4.2

Chart 4.1

Figure 4.4

Figure 4.5

Figure 4.6

Scheme 4.3

Scheme 4.4

Scheme 4.5

Figure 4.7

Figure 4.8

Scheme 4.6

Figure 4.9

Figure 4.10

Figure 4.11

Figure 4.12

Figure 4.13

Figure 4.14

Scheme 4.7

Scheme 4.8

Figure 4.15

Figure 4.16

Scheme 5.1

Figure 5.1

Figure 5.2

Chart 5.1

Scheme 5.2

Figure 5.3

Chart 5.2

Scheme 5.3

Scheme 5.4

Figure 5.4

Scheme 5.5

Scheme 5.6

Scheme 5.7

Scheme 5.8

Scheme 5.9

Scheme 5.10

Scheme 5.11

Scheme 5.12

Scheme 6.1

Scheme 6.2

Scheme 6.3

Scheme 6.4

Scheme 6.5

Scheme 6.6

Scheme 6.7

Figure 6.1

Figure 6.2

Scheme 6.8

Scheme 6.9

Figure 6.3

Scheme 6.10

Figure 6.4

Scheme 6.11

Scheme 6.12

Scheme 6.13

Scheme 6.14

Scheme 6.15

Scheme 6.16

Figure 6.5

Scheme 6.17

Figure 6.6

Scheme 6.18

Scheme 6.19

Chart 6.1

Scheme 6.20

Scheme 6.21

Figure 6.7

Scheme 6.22

Figure 6.8

Scheme 6.23

Figure 6.9

Figure 6.10

Scheme 7.1

Scheme 7.2

Scheme 7.3

Scheme 7.4

Figure 7.1

Figure 7.2

Figure 7.3

Scheme 7.5

Figure 7.4

Scheme 7.6

Figure 7.5

Figure 7.6

Figure 7.7

Figure 7.8

Figure 7.9

Figure 7.10

Scheme 7.7

Scheme 7.8

Figure 7.11

Scheme 7.9

Figure 7.12

Scheme 7.10

Figure 7.13

Scheme 7.11

Figure 7.14

Scheme 7.12

Figure 7.15

Figure 7.16

Scheme 7.13

Figure 7.17

Figure 7.18

Scheme 7.14

Figure 7.19

Figure 7.20

Chart 8.1

Figure 8.1

Figure 8.2

Chart 8.2

Scheme 8.1

Scheme 8.2

Figure 8.3

Scheme 8.3

Scheme 8.4

Chart 8.3

Chart 8.4

Scheme 8.5

Figure 8.4

Scheme 8.6

Chart 8.5

Scheme 8.7

Scheme 8.8

Scheme 8.9

Scheme 8.10

Scheme 8.11

Scheme 8.12

Scheme 8.13

Scheme 8.14

Scheme 8.15

Scheme 8.16

Chart 8.6

Chart 8.7

Chart 8.8

Scheme 8.17

Figure 8.5

Scheme 8.18

Scheme 8.19

Scheme 8.20

Scheme 9.1

Scheme 9.2

Scheme 9.3

Figure 9.1

Scheme 9.4

Scheme 9.5

Chart 9.1

Scheme 9.6

Scheme 9.7

Figure 9.2

Figure 9.3

Scheme 9.8

Chart 9.2

Scheme 9.9

Scheme 9.10

Scheme 9.11

Scheme 9.12

Scheme 9.13

Scheme 9.14

Scheme 9.15

Scheme 9.16

Scheme 9.17

Scheme 9.18

Scheme 9.19

Scheme 9.20

Figure 9.4

Scheme 9.21

Scheme 9.22

Scheme 9.23

Scheme 9.24

Scheme 9.25

Scheme 9.26

Scheme 9.27

Scheme 9.28

Scheme 9.29

Scheme 9.30

Scheme 9.31

Scheme 9.32

Figure 9.5

Scheme 9.33

Figure 9.6

Scheme 9.34

Scheme 9.35

Scheme 9.36

Scheme 9.37

Scheme 9.38

Scheme 9.39

Scheme 9.40

Scheme 9.41

Scheme 9.42

Scheme 9.43

Scheme 9.44

Scheme 9.45

Scheme 9.46

Figure 9.7

Scheme 9.47

Scheme 9.48

Scheme 9.49

Scheme 9.50

Scheme 9.51

Scheme 9.52

Scheme 9.53

Scheme 9.54

Scheme 9.55

Scheme 9.56

Scheme 9.57

Scheme 9.58

Figure 9.8

Scheme 9.59

Scheme 9.60

Scheme 9.61

Scheme 9.62

Scheme 9.63

Scheme 9.64

Scheme 10.1

Figure 10.1

Figure 10.2

Scheme 10.2

Chart 10.1

Scheme 10.3

Scheme 10.4

Figure 10.3

Scheme 10.5

Scheme 10.6

Figure 10.4

Figure 10.5

Scheme 10.7

Scheme 10.8

Scheme 10.9

Scheme 10.10

Scheme 10.11

Scheme 10.12

Figure 10.6

Scheme 10.13

Figure 10.7

Figure 10.8

Scheme 10.14

Scheme 10.15

Scheme 10.16

Scheme 10.17

Scheme 10.18

Scheme 10.19

Scheme 10.20

Scheme 10.21

Scheme 10.22

Scheme 10.23

Scheme 10.24

Scheme 10.25

Scheme 10.26

Scheme 10.27

Scheme 10.28

Scheme 10.29

Scheme 10.30

Scheme 10.31

Scheme 10.32

Scheme 10.33

Scheme 10.34

Scheme 10.35

Scheme 10.36

Scheme 10.37

Scheme 10.38

Scheme 10.39

Figure 11.1

Chart 11.1

Scheme 11.1

Scheme 11.2

Figure 11.2

Figure 11.3

Chart 11.2

Figure 11.4

Figure 11.5

Figure 11.6

Figure 11.7

Figure 11.8

Figure 11.9

Figure 11.10

Figure 11.11

Figure 11.12

Figure 11.13

Figure 11.14

Figure 11.15

Figure 11.16

Figure 11.17

Figure 11.18

Figure 11.19

Figure 11.20

Figure 11.21

Scheme 11.3

Figure 11.22

Scheme 11.4

Scheme 11.5

Scheme 11.6

Scheme 11.7

Scheme 11.8

Scheme 11.9

Scheme 11.10

Figure 11.23

Scheme 11.11

Scheme 11.12

Scheme 11.13

Scheme 11.14

Figure 11.24

Scheme 11.15

Scheme 11.16

Scheme 11.17

Figure 11.25

Scheme 11.18

Scheme 11.19

Figure 11.26

Scheme 11.20

Scheme 11.21

Figure 11.27

Scheme 11.22

Scheme 11.23

Figure 11.28

Figure 11.29

Scheme 11.24

Figure 11.30

Scheme 11.25

Scheme 11.26

Figure 11.31

Scheme 11.27

Figure 11.32

Scheme 11.28

Figure 11.33

Scheme 11.29

Scheme 11.30

Scheme 11.31

Scheme 11.32

Scheme 12.1

Scheme 12.2

Chart 12.1

Figure 12.1

Chart 12.2

Scheme 12.3

Figure 12.2

Scheme 12.4

Scheme 12.5

Figure 12.3

Figure 12.4

Figure 12.5

Chart 12.3

Scheme 12.6

Scheme 12.7

Scheme 12.8

Scheme 12.9

Scheme 12.10

Figure 12.6

Scheme 12.11

Scheme 12.12

Scheme 12.13

Scheme 12.14

Figure 12.7

Chart 12.4

Scheme 12.15

Scheme 12.16

Scheme 12.17

Figure 12.8

Scheme 12.18

Scheme 12.19

Scheme 12.20

Scheme 12.21

Scheme 12.22

Scheme 12.23

Scheme 12.24

Scheme 12.25

Scheme 12.26

Chart 12.5

Scheme 12.27

Figure 12.9

Chart 12.6

Chart 12.7

Figure 12.10

Figure 12.11

Scheme 12.28

Chart 12.8

Chart 12.9

Scheme 12.29

Scheme 12.30

Scheme 12.31

Scheme 12.32

Scheme 12.33

Scheme 12.34

Chart 12.10

Chart 12.11

Scheme 12.35

Scheme 12.36

Scheme 12.37

Scheme 12.38

Figure 12.12

Scheme 12.39

Scheme 12.40

Scheme 12.41

Scheme 12.42

Figure 13.1

Scheme 13.1

Figure 13.2

Figure 13.3

Scheme 13.2

Scheme 13.3

Scheme 13.4

Scheme 13.5

Scheme 13.6

Scheme 13.7

Scheme 13.8

Scheme 13.9

Scheme 13.10

Scheme 13.11

Scheme 13.12

Scheme 13.13

Scheme 13.14

Scheme 13.15

Scheme 13.16

Scheme 13.17

Scheme 13.18

Scheme 13.19

Scheme 13.20

Scheme 13.21

Scheme 13.22

Chart 13.1

Scheme 13.23

Scheme 13.24

Scheme 13.25

Scheme 13.26

Scheme 13.27

Scheme 13.28

Chart 13.2

Scheme 13.29

Chart 13.3

Scheme 13.30

Scheme 13.31

Scheme 13.32

Figure 13.4

Scheme 13.33

Scheme 13.34

Scheme 13.35

Scheme 13.36

Scheme 13.37

Scheme 13.38

Scheme 13.39

Chart 13.4

Scheme 13.40

Scheme 13.41

Scheme 13.42

Scheme 13.43

Scheme 13.44

Scheme 13.45

Scheme 13.46

Scheme 13.47

Scheme 13.48

Scheme 13.49

Scheme 13.50

Scheme 13.51

Scheme 13.52

Scheme 13.53

Scheme 13.54

Scheme 13.55

Scheme 13.56

Scheme 13.57

Scheme 13.58

Scheme 13.59

Scheme 13.60

Scheme 13.61

Scheme 13.62

Scheme 13.63

Scheme 13.64

Scheme 13.65

Scheme 13.66

Scheme 13.67

Scheme 13.68

Scheme 13.69

Scheme 13.70

Scheme 13.71

Scheme 13.72

Scheme 13.73

Scheme 13.74

Scheme 13.75

Scheme 13.76

Scheme 13.77

Scheme 13.78

Scheme 13.79

Scheme 13.80

Scheme 13.81

Scheme 13.82

Scheme 13.83

Scheme 13.84

Scheme 13.85

Scheme 13.86

Scheme 13.87

Scheme 13.88

Scheme 13.89

Scheme 13.90

Scheme 13.91

Scheme 13.92

Scheme 13.93

Scheme 13.94

Scheme 13.95

Scheme 13.96

Scheme 13.97

Scheme 13.98

Scheme 13.99

Scheme 13.100

Scheme 13.101

Scheme 13.102

Scheme 13.103

Scheme 13.104

Scheme 13.105

Scheme 13.106

Scheme 13.107

Scheme 13.108

Figure 13.5

Scheme 13.109

Scheme 13.110

Scheme 13.111

Scheme 13.112

Scheme 13.113

Scheme 13.114

Scheme 13.115

Scheme 13.116

Scheme 13.117

Scheme 13.118

Scheme 13.119

Scheme 13.120

Scheme 13.121

Scheme 13.122

Scheme 13.123

Scheme 13.124

Scheme 13.125

Scheme 13.126

Scheme 13.127

Scheme 13.128

Figure 13.6

Figure 13.7

Scheme 13.129

Scheme 13.130

Scheme 13.131

Scheme 13.132

Scheme 13.133

Scheme 13.134

Figure 13.8

Scheme 13.135

Scheme 13.136

Scheme 13.137

Scheme 13.138

Scheme 13.139

Scheme 13.140

Figure 13.9

Scheme 13.141

Scheme 13.142

Scheme 14.1

Scheme 14.2

Scheme 14.3

Scheme 14.4

Scheme 14.5

Scheme 14.6

Scheme 14.7

Scheme 14.8

Scheme 14.9

Scheme 14.10

Scheme 14.11

Scheme 14.12

Scheme 14.13

Scheme 14.14

Scheme 14.15

Scheme 14.16

Scheme 14.17

Scheme 14.18

Scheme 14.19

Scheme 14.20

Scheme 14.21

Scheme 14.22

Scheme 14.23

Scheme 14.24

Scheme 14.25

Scheme 14.26

Chart 14.1

Scheme 14.27

Figure 14.1

Scheme 14.28

Scheme 14.29

Scheme 14.30

Scheme 14.31

Scheme 14.32

Scheme 14.33

Scheme 14.34

Figure 14.2

Scheme 14.35

Scheme 14.36

Scheme 14.37

Scheme 14.38

Scheme 14.39

Scheme 14.40

Scheme 14.41

Scheme 14.42

Scheme 14.43

Scheme 14.44

Scheme 14.45

Scheme 14.46

Scheme 14.47

Scheme 14.48

Scheme 14.49

Scheme 14.50

Scheme 14.51

Scheme 14.52

Scheme 14.53

Scheme 14.54

Scheme 14.55

Scheme 14.56

Scheme 14.57

Scheme 14.58

Scheme 14.59

Scheme 14.60

Scheme 14.61

Scheme 15.1

Scheme 15.2

Scheme 15.3

Scheme 15.4

Scheme 15.5

Scheme 15.6

Scheme 15.7

Scheme 15.8

Scheme 15.9

Scheme 15.10

Scheme 15.11

Scheme 15.12

Scheme 15.13

Scheme 15.14

Scheme 15.15

Scheme 15.16

Scheme 15.17

Scheme 15.18

Scheme 15.19

Scheme 15.20

Scheme 15.21

Scheme 15.22

Scheme 15.23

Scheme 15.24

Scheme 15.25

Scheme 15.26

Scheme 15.27

Scheme 15.28

Scheme 15.29

Scheme 15.30

Scheme 15.31

Scheme 15.32

Scheme 15.33

Scheme 15.34

Scheme 15.35

Scheme 15.36

Scheme 15.37

Scheme 15.38

Scheme 15.39

Scheme 15.40

Scheme 15.41

Scheme 15.42

Scheme 15.43

Scheme 15.44

Scheme 15.45

Scheme 15.46

Scheme 15.47

Scheme 15.48

Scheme 15.49

Scheme 15.50

Scheme 15.51

Scheme 15.52

Scheme 15.53

Scheme 15.54

Scheme 15.55

Scheme 15.56

Scheme 15.57

Scheme 15.58

Scheme 15.59

Scheme 15.60

Scheme 15.61

Scheme 16.1

Chart 16.1

Figure 16.1

Scheme 16.2

Scheme 16.3

Figure 16.2

Scheme 16.4

Figure 16.3

Figure 16.4

Figure 16.5

Figure 16.6

Figure 16.7

Figure 16.8

Figure 16.9

Scheme 16.5

Figure 16.10

Scheme 16.6

Figure 16.11

Scheme 16.7

Figure 16.12

Figure 16.13

Scheme 16.8

Figure 16.14

Figure 16.15

Scheme 16.9

Figure 16.16

Figure 16.17

Figure 16.18

Figure 16.19

Scheme 16.10

Scheme 16.11

Scheme 16.12

Figure 16.20

Scheme 16.13

Figure 16.21

Scheme 17.1

Figure 17.1

Figure 17.2

Figure 17.3

Scheme 17.2

Scheme 17.3

Scheme 17.4

Figure 17.4

Scheme 17.5

Figure 17.5

Scheme 17.6

Figure 17.6

Scheme 17.7

Scheme 17.8

Figure 17.7

Scheme 17.9

Scheme 17.10

Figure 17.8

Scheme 17.11

Scheme 17.12

Scheme 17.13

Scheme 17.14

Scheme 17.15

Scheme 17.16

Scheme 17.17

Scheme 17.18

Scheme 17.19

Scheme 17.20

Scheme 17.21

Scheme 17.22

Scheme 17.23

Scheme 17.24

Scheme 17.25

Scheme 17.26

Scheme 17.27

Scheme 17.28

Scheme 17.29

Scheme 17.30

Figure 17.9

Scheme 17.31

Scheme 17.32

Scheme 17.33

Figure 17.10

Scheme 18.1

Chart 18.1

Scheme 18.2

Chart 18.2

Scheme 18.3

Scheme 18.4

Chart 18.3

Scheme 18.5

Chart 18.4

Scheme 18.6

Scheme 18.7

Scheme 18.8

Scheme 18.9

Scheme 18.10

Scheme 18.11

Scheme 18.12

Chart 18.5

Scheme 18.13

Scheme 18.14

Scheme 18.15

Scheme 18.16

Scheme 18.17

Scheme 18.18

Scheme 18.19

Scheme 18.20

Scheme 18.21

Scheme 18.22

Scheme 18.23

Scheme 18.24

Scheme 18.25

Scheme 18.26

Scheme 18.27

Scheme 18.28

Scheme 18.29

Scheme 18.30

Scheme 18.31

Scheme 18.32

Scheme 18.33

Scheme 18.34

Scheme 18.35

Scheme 18.36

Scheme 18.37

Scheme 18.38

Scheme 18.39

Scheme 18.40

Scheme 18.41

Scheme 18.42

Scheme 18.43

Scheme 18.44

Scheme 18.45

Scheme 18.46

Scheme 18.47

Scheme 18.48

Scheme 18.49

Scheme 18.50

Scheme 18.51

Scheme 18.52

Scheme 18.53

Scheme 18.54

Scheme 18.55

Scheme 18.56

Scheme 18.57

Scheme 18.58

Scheme 18.59

Scheme 18.60

Scheme 18.61

Scheme 18.62

Scheme 18.63

Scheme 18.64

Scheme 18.65

Scheme 18.66

Scheme 18.67

Scheme 18.68

Scheme 18.69

Scheme 18.70

Scheme 18.71

Scheme 18.72

Scheme 18.73

Scheme 18.74

Scheme 18.75

Scheme 18.76

Scheme 18.77

Scheme 18.78

Scheme 18.79

Scheme 18.80

Scheme 18.81

Scheme 18.82

Scheme 18.83

Scheme 18.84

Scheme 18.85

Scheme 18.86

Scheme 18.87

Scheme 18.88

Scheme 19.1

Scheme 19.2

Scheme 19.3

Scheme 19.4

Scheme 19.5

Scheme 19.6

Scheme 19.7

Scheme 19.8

Scheme 19.9

Scheme 19.10

Scheme 19.11

Scheme 19.12

Scheme 19.13

Scheme 19.14

Scheme 19.15

Scheme 19.16

Scheme 19.17

Scheme 19.18

Scheme 19.19

Scheme 19.20

Scheme 19.21

Scheme 19.22

Scheme 19.23

Scheme 19.24

Scheme 19.25

Scheme 19.26

Scheme 19.27

Scheme 19.28

Scheme 19.29

Scheme 19.30

Scheme 19.31

Scheme 19.32

Scheme 20.1

Scheme 20.2

Scheme 20.3

Scheme 20.4

Chart 20.1

Chart 20.2

Chart 20.3

Chart 20.4

Chart 20.5

Scheme 20.5

Scheme 20.6

Scheme 20.7

Scheme 20.8

Scheme 20.9

Scheme 20.10

Scheme 20.11

Scheme 20.12

Scheme 20.13

Scheme 20.14

Scheme 20.15

Scheme 21.1

Scheme 21.2

Scheme 21.3

Scheme 21.4

Figure 21.1

Scheme 21.5

Scheme 21.6

Figure 21.2

Scheme 21.7

Figure 21.3

Scheme 21.8

Figure 21.4

Scheme 21.9

Scheme 21.10

Scheme 21.11

Scheme 21.12

Scheme 21.13

Scheme 21.14

Scheme 21.15

Scheme 21.16

Scheme 21.17

Scheme 21.18

Scheme 21.19

Scheme 21.20

Scheme 21.21

Scheme 21.22

Scheme 21.23

Scheme 21.24

Scheme 21.25

Scheme 21.26

Scheme 21.27

Figure 21.5

Scheme 22.1

Scheme 22.2

Scheme 22.3

Chart 22.1

Chart 22.2

Chart 22.3

Chart 22.4

Scheme 22.4

Chart 22.5

Scheme 22.5

Chart 22.6

Chart 22.7

Chart 22.8

Chart 22.9

Chart 22.10

Chart 22.11

Chart 22.12

Chart 22.13

Chart 22.14

Figure 22.1

Scheme 22.6

Scheme 22.7

Scheme 22.8

Scheme 22.9

Scheme 22.10

Figure 22.2

Scheme 22.11

Scheme 22.12

Chart 22.15

Scheme 22.13

Scheme 22.14

Scheme 23.1

Figure 23.1

Scheme 23.2

Scheme 23.3

Figure 23.2

Scheme 23.4

Scheme 23.5

Scheme 23.6

Scheme 23.7

Scheme 23.8

Scheme 23.9

Scheme 23.10

Scheme 23.11

Scheme 23.12

Scheme 23.13

Scheme 23.14

Scheme 23.15

Scheme 23.16

Scheme 23.17

Scheme 23.18

Scheme 23.19

Scheme 23.20

Scheme 23.21

Scheme 23.22

Figure 23.3

Figure 23.4

Figure 23.5

Figure 23.6

Figure 23.7

Figure 23.8

Scheme 23.23

Scheme 23.24

Figure 23.9

Scheme 23.25

Scheme 23.26

Scheme 24.1

Scheme 24.2

Scheme 24.3

Scheme 24.4

Scheme 24.5

Scheme 24.6

Scheme 24.7

Scheme 24.8

Scheme 24.9

Scheme 24.10

Scheme 24.11

Scheme 24.12

Scheme 24.13

Scheme 24.14

Scheme 24.15

Figure 24.1

Scheme 24.16

Scheme 24.17

Scheme 24.18

Scheme 24.19

Scheme 24.20

Scheme 24.21

Scheme 24.22

Scheme 24.23

Scheme 24.24

Scheme 24.25

Scheme 24.26

Scheme 24.27

Scheme 24.28

Figure 24.2

Scheme 24.29

Scheme 24.30

Scheme 24.31

Figure 24.3

Scheme 24.32

Scheme 24.33

Scheme 24.34

Scheme 24.35

Scheme 24.36

Scheme 24.37

Figure 24.4

Figure 24.5

Scheme 24.38

Scheme 24.39

Scheme 24.40

Scheme 24.41

Scheme 24.42

Scheme 24.43

Scheme 24.44

Scheme 24.45

Scheme 24.46

Scheme 24.47

Scheme 24.48

Scheme 24.49

Scheme 24.50

Scheme 24.51

Scheme 24.52

Scheme 24.53

Figure 25.1

Figure 25.2

Scheme 25.1

Figure 25.3

Scheme 25.2

Scheme 25.3

Figure 25.4

Scheme 25.4

Figure 25.5

Scheme 25.5

Scheme 25.6

Figure 25.6

Figure 25.7

Scheme 25.7

Figure 25.8

Figure 25.9

Scheme 25.8

Scheme 25.9

Figure 25.10

Scheme 25.10

Scheme 25.11

Scheme 25.12

Scheme 25.13

Scheme 25.14

Figure 25.11

Scheme 25.15

Figure 25.12

Chart 25.1

Scheme 25.16

Figure 25.13

Scheme 25.17

Scheme 25.18

Figure 25.14

Figure 25.15

Scheme 25.19

Scheme 25.20

Scheme 25.21

Scheme 25.22

Figure 25.16

Scheme 25.23

Scheme 25.24

Scheme 25.25

Scheme 25.26

Scheme 25.27

Scheme 25.28

Scheme 25.29

Scheme 25.30

Scheme 25.31

Figure 25.17

Scheme 25.32

Scheme 25.33

Scheme 25.34

Scheme 25.35

Figure 25.18

Scheme 25.36

Figure 25.19

Scheme 25.37

Scheme 25.38

Scheme 25.39

Scheme 25.40

Scheme 26.1

Figure 26.1

Scheme 26.2

Figure 26.2

Scheme 26.3

Scheme 26.4

Scheme 26.5

Scheme 26.6

Scheme 26.7

Scheme 26.8

Scheme 26.9

Figure 26.3

Scheme 26.10

Scheme 26.11

Scheme 26.12

Scheme 26.13

Scheme 26.14

Scheme 26.15

Scheme 26.16

Figure 26.4

Scheme 26.17

Scheme 26.18

Figure 26.5

Scheme 26.19

Scheme 26.20

Scheme 26.21

Scheme 26.22

Scheme 26.23

Scheme 26.24

Scheme 26.25

Scheme 26.26

Scheme 26.27

Figure 27.1

Figure 27.2

Figure 27.3

Scheme 27.1

Chart 27.1

Chart 27.2

Scheme 27.2

Scheme 27.3

Scheme 27.4

Figure 27.4

Scheme 27.5

Scheme 27.6

Figure 27.5

Scheme 27.7

Scheme 27.8

Scheme 27.9

Scheme 27.10

Scheme 27.11

Scheme 27.12

Scheme 27.13

Scheme 27.14

Scheme 27.15

Scheme 27.16

Scheme 27.17

Scheme 27.18

Scheme 27.19

Scheme 27.20

Scheme 27.21

Scheme 27.22

Scheme 27.23

Scheme 27.24

Scheme 27.25

Scheme 27.26

Scheme 27.27

Scheme 27.28

Scheme 27.29

Scheme 27.30

Scheme 27.31

Scheme 27.32

Scheme 27.33

Scheme 27.34

Figure 27.6

Scheme 27.35

Scheme 27.36

Scheme 27.37

Scheme 27.38

Scheme 27.39

Scheme 27.40

Scheme 27.41

Scheme 27.42

Scheme 27.43

Scheme 27.44

Scheme 27.45

Scheme 27.46

Scheme 27.47

Scheme 27.48

Scheme 27.49

Scheme 27.50

Scheme 27.51

Scheme 27.52

Scheme 27.53

Scheme 27.54

Scheme 27.55

Scheme 27.56

Scheme 27.57

Scheme 27.58

Scheme 27.59

Scheme 27.60

Scheme 27.61

Scheme 27.62

Scheme 27.63

Scheme 27.64

Scheme 27.65

Scheme 27.66

Scheme 27.67

Scheme 27.68

Guide

Cover

Table of Contents

Begin Reading

Part 1

Chapter 1

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Edwin Vedejs and Scott E. Denmark

Lewis Base Catalysis in Organic Synthesis

Volume 1, 2 and 3

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

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The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.

© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.

Print ISBN: 978-3-527-33618-0

ePDF ISBN: 978-3-527-67515-9

ePub ISBN: 978-3-527-67517-3

Mobi ISBN: 978-3-527-67516-6

oBook ISBN: 978-3-527-67514-2

Preface for Volumes 1–3

This three-volume book originates from a widely cited 2008 review with the same title, Lewis Base Catalysis in Organic Synthesis, coauthored by Denmark and Beutner. Given the interest generated by that article, as well as the explosion of related topics in the literature, a more comprehensive treatment was desired by Wiley-VCH. Scott Denmark declined taking on the current project as sole editor due to extensive prior commitments, but did agree to serve as coeditor in planning the project and determining scientific content. In addition, he edited Chapter 1, authored several of the later chapters, and wrote the Introduction that traces definitions of catalysis from Ostwald to the current era and presents an updated, broadly inclusive definition that is used in the current volumes.

After extensive discussion by both coeditors during the planning stages, the decision was made to emphasize mechanistic aspects of Lewis base catalysis where possible, and to provide broad coverage of the most important preparative advances with sufficient commentary and explanation to facilitate graduate instruction as well as to stimulate new research initiatives. Another important objective was to remind the current generation of the remarkable insight and contributions of G.N. Lewis. He was the first to recognize the possibility of catalysis by electron pair donors, and did so two decades before independent attempts to classify this family of reactions resulted in the alternative terminology “nucleophilic catalysis.” For historical as well as heuristic and conceptual reasons, it is better and more correct to regard this chemistry as Lewis base catalysis.

All of the examples of Lewis base catalysis in these volumes feature activation by a key bonding event between a substrate acceptor orbital (classified as n*, π*, or σ* in chapter headings) and two electrons from a donor orbital in the Lewis base catalyst, but this donor–acceptor interaction is only the appetizer. The main course consists of the stages that follow the Lewis base activation step, and the menu of mechanistic options can be incredibly rich. The options can be very simple, as in halide catalysis (Chapter 1) where a single activation stage by the halide Lewis base is usually followed by a single product-forming stage. However, such mechanistic simplicity is the exception. More often, the mechanisms are deceptively simple, multifaceted, and amazingly subtle. Even that familiar undergraduate-level example of Lewis base catalysis, the venerable benzoin condensation, can be challenging for students who must confront multiple conceptual layers (reversible nucleophilic addition of cyanide; acid–base concepts; carbanion delocalization; leaving group ability) and decipher several steps following the activation stage. It is worth recalling that an earlier mechanism for the benzoin condensation proposed the dimerization of “PhC(OH)” (yes, the hydroxyl carbene tautomer of benzaldehyde!) to the intermediate enediol PhC(OH)=C(OH)Ph (Bredig, 1904). This suggestion was perfectly logical, concise, and plausible at the time, but lasted only until the alternatives were considered and the mechanism was studied. Perhaps a similar fate awaits other plausible mechanisms, a phrase that appears often in these volumes.

By now, many of the fundamental principles underlying Lewis base catalysis have indeed been studied, and several of the most extensively investigated topics are featured in Volume 1. Chapter 1 begins with a historical account tracing key highlights in the development of catalysis, including important contributions by Berzelius, Liebig, Ostwald, and other major figures of nineteenth century chemistry. This chapter also mentions milestones in Lewis base catalysis from 1834 to 1970, and briefly comments on a few more recent developments that await detailed investigation.

Lewis was the first to recognize the electronic features that define Lewis base catalysis (Introduction and Chapter 2). An overview of his profound insight is presented in Chapter 2, which traces the evolution of Lewis's landmark formulation of the electronic theory of structure and bonding to a clear assertion that his (Lewis's) bases possess every property ascribed to Brønsted bases, including their ability to act as catalysts. The Lewis concepts benefited greatly from refinement and popularization by Mulliken and Jensen, who helped to develop the unifying conceptual basis, a classification scheme of reaction types according to relevant orbital interactions, and a generally applicable terminology that serves as the organizational framework for these volumes.

The next two chapters focus on the thermodynamic and kinetic aspects of Lewis base catalysis, respectively. Chapter 3 presents the classical methods that have been used to quantify Lewis basicity of the most important Lewis bases, and defines the concepts of Lewis Affinity and Basicity. Extensive discussion and tables compare Lewis bases using representative affinity parameters, including those for various cations (proton, methyl, lithium) and neutral Lewis acids (BF3, iodine, 4-fluorophenol). Similarly, Chapter 4 quantifies the corresponding kinetic component (nucleophilicity) using the Mayr Scale, introduces the related concepts of electrofugality and nucleofugality, and provides examples of how these concepts are used by synthetic chemists.

The selection of topics for the subsequent chapters of Volume 1 was made according to several criteria: (i) extensive in-depth mechanistic study, (ii) preparative importance, and (iii) mechanistic diversity following attack by the Lewis base. The first of these chapters (Chapter 5) takes on acyl transfer catalysis by pyridine derivatives, a topic that has been studied in sufficient depth to develop a mechanism that is well understood and widely accepted. Perhaps the same can now be said for much of Chapter 6, involving the mechanism for proline-catalyzed carbonyl activation in enantioselective synthesis, but this is complex, broadly applicable chemistry and the evaluation of models for enantioselection often depends on computational methods that are still undergoing refinement. Similar concerns regarding computations arise in reactions where complexity is associated with the timing and nature of proton transfer events, or with the role of various additives. Those scenarios have long confounded attempts to fully understand the mechanism of the Morita–Baylis–Hillman reaction, a topic that is summarized in Chapter 7. Progress has been made using sophisticated mechanistic tools based on kinetics, mass spectroscopy, computation, and acid–base relationships, but developing a generally applicable mechanism has proven to be difficult.

Some of the mechanistically most intriguing examples of Lewis base catalysis are featured in Chapters 8–11 of Volume 1. These chapters describe reactions that begin with a bonding interaction between the Lewis base and the σ* or n* (unoccupied p) orbitals of the electrophile, reactions that proceed with astonishing mechanistic diversification, even in the relatively simple context of Lewis base activation of silicon nucleophiles (Chapter 8