Nitroalkanes

Synthesis, Reactivity, and Applications
1. Auflage 2021
ISBN: 978-3-527-34745-2
Verlag: Wiley-VCH GmbH

Buch, Englisch, 298 Seiten, Format (B × H): 173 mm x 247 mm, Gewicht: 750 g

Aimed at synthetic organic chemists in academia and industry, the book summarizes recent developments in the preparation of nitroalkanes, their functionalization, and application for the synthesis of important heterocycles, natural products, and bioactive compounds.

Autoren/Hrsg.

Ballini, Roberto

Palmieri, Alessandro

Fachgebiete

• Naturwissenschaften Chemie Chemie Allgemein Pharmazeutische Chemie, Medizinische Chemie
• Technische Wissenschaften Verfahrenstechnik | Chemieingenieurwesen | Biotechnologie Verfahrenstechnik, Chemieingenieurwesen
• Naturwissenschaften Chemie Organische Chemie

Inhaltsverzeichnis

About the Authors xiii

Acknowledgments xv

Introduction xvii

List of Abbreviations xix

1 Synthesis of Nitroalkanes 1

1.1 Synthesis of Nitroalkanes 1

1.1.1 Displacement of Alkyl Halides 1

1.2 Nitration of Mesylates and Tosylates 4

1.3 Oxidation of Nitrogen Derivatives 5

1.3.1 Oxidation of Amines 5

1.3.2 Oxidation of Oximes 7

1.3.3 Oxidation of Azides 8

1.4 Reduction of Conjugate Nitroalkenes 8

1.4.1 Reduction of Nitroalkenes into Nitroalkanes 8

1.4.2 Stereoselective Reduction of Conjugated Nitroalkenes 10

1.4.3 Aldehyde Reductive Nitromethylation 10

1.5 Nitration of Alkanes 11

1.6 Metal-Catalyzed Alkylation or Arylation of Nitroalkanes 11

1.6.1 Nitroalkylation of Aryl Halides 12

1.6.2 Nitroalkylation of Allylic Esters 13

1.6.3 Nitroalkylation of Allylic Alcohols 13

1.6.4 Two-Carbon Homologation of Vinyl Triflates and Bromides 15

References 16

2 Reduction of the Nitro Group into Amines 19

2.1 Representative Synthetic Applications of Nitroalkane Reductions 24

2.1.1 Reduction of Nitroalkanes Obtained via Nitroaldol Reaction 24

2.1.2 Reduction of Nitroalkanes Obtained via Michael Reaction 26

References 28

3 Nitro Group to Carbonyl (Nef Reaction) 31

3.1 Nef Reaction under Oxidative Conditions 31

3.1.1 Method Ox1 31

3.1.2 Method Ox2 31

3.1.3 Method Ox3 32

3.1.4 Method Ox4 33

3.1.5 Method Ox5 34

3.1.6 Method Ox6 34

3.1.7 Method Ox7 34

3.1.8 Method Ox8 35

3.1.9 Method Ox9 36

3.1.10 Method Ox10 37

3.1.11 Method Ox11 37

3.1.12 Method Ox12 38

3.1.13 Method Ox13 38

3.1.14 Method Ox14 38

3.1.15 Method Ox15 39

3.1.16 Method Ox16 40

3.1.17 Method Ox17 40

3.2 Nef Reaction Under Reductive Conditions 41

3.2.1 Method Red1 41

3.2.2 Method Red2 42

3.2.3 Method Red3 43

3.2.4 Method Red4 43

3.3 Nef Reaction Under Basic Conditions 44

3.3.1 Method Base1 44

3.3.2 Method Base2 45

3.4 Other Methods for the Nef Reaction 46

3.4.1 Method by NaNO2 46

3.4.2 Method by Me3SiCl 47

3.4.3 Method by SiO2/TBD 48

3.5 Synthetic Applications of the Nef Reaction (Representative Examples) 49

3.5.1 Solvolytic Methods 49

3.5.2 Oxidative Methods 50

3.5.3 Reductive Methods 52

3.5.4 Basic Methods 54

3.5.5 NaNO2 Methods 55

References 57

4 Nitroaldol (Henry) Reaction 59

4.1 General Catalysts and Promoters 60

4.1.1 Heterogeneous Catalysts and Promoters 60

4.1.2 Green Solvents 66

4.1.2.1 Nitroaldol Reaction inWater 67

4.1.2.2 Nitroaldol Reaction in Ionic Liquids 70

4.2 Nitroaldol Condensation 72

4.2.1 Application of General Henry Reaction 75

4.3 Asymmetric Henry Reaction 82

4.4 Aza-Henry Reaction 91

4.4.1 Aza-Henry Reaction via N-Protected Imines 92

4.4.2 Aza-Henry Reaction via a-Amidosulfones 96

References 102

5 Conjugate Addition of Nitroalkanes to Electron-Poor Alkenes (Michael Reaction) 107

5.1 General Homogeneous Procedures 107

5.2 Heterogeneous Procedures 109

5.3 Michael Reaction under Green Solvents 114

5.4 Asymmetric Michael Reaction 117

5.4.1 Asymmetric Michael Reaction with Enones 117

5.4.2 Asymmetric Michael Reaction with Enals 123

5.4.3 Asymmetric Michael Reaction with a,ß-Unsaturated Esters 126

5.4.4 Asymmetric Michael Reaction with Conjugate Nitroalkenes 126

5.4.5 Asymmetric Michael Reaction with Vinyl Sulfones 128

5.5 Synthetic Applications of Michael Reaction 129

References 138

6 Formation of C—C Bond by Coupling Nitroalkanes with Aryl Halides 141

6.1 Main Procedures for Coupling Nitroalkanes

Über Autor(innen)

Roberto Ballini is Professor of Organic Chemistry at the University of Camerino in Italy. His research focus is on organic synthesis, with a particular emphasis on aliphatic nitro compounds. He has published over 250 scientific articles and edited two books.

Alessandro Palmieri is Associate Professor at the University of Camerino in Italy. His research focus is on eco-friendly processes for the formation of C-C and C-X bonds and flow chemical protocols for the synthesis of fine chemicals. He has published over 100 scientific articles.