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Table of Contents
List of Tables
List of Illustrations
Guide
Pages
Nitroalkanes. Synthesis, Reactivity, and Applications
About the Authors
Acknowledgments
Introduction
Reference
List of Abbreviations
1 Synthesis of Nitroalkanes. 1.1 Synthesis of Nitroalkanes
1.1.1 Displacement of Alkyl Halides
1.2 Nitration of Mesylates and Tosylates
1.3 Oxidation of Nitrogen Derivatives
1.3.1 Oxidation of Amines
1.3.2 Oxidation of Oximes
1.3.3 Oxidation of Azides
1.4 Reduction of Conjugate Nitroalkenes
1.4.1 Reduction of Nitroalkenes into Nitroalkanes
1.4.2 Stereoselective Reduction of Conjugated Nitroalkenes
1.4.3 Aldehyde Reductive Nitromethylation
1.5 Nitration of Alkanes
1.6 Metal-Catalyzed Alkylation or Arylation of Nitroalkanes
1.6.1 Nitroalkylation of Aryl Halides
1.6.2 Nitroalkylation of Allylic Esters
1.6.3 Nitroalkylation of Allylic Alcohols
1.6.4 Two-Carbon Homologation of Vinyl Triflates and Bromides
References
2 Reduction of the Nitro Group into Amines
2.1 Representative Synthetic Applications of Nitroalkane Reductions
2.1.1 Reduction of Nitroalkanes Obtained via Nitroaldol Reaction
2.1.2 Reduction of Nitroalkanes Obtained via Michael Reaction
References
3 Nitro Group to Carbonyl (Nef Reaction)
3.1 Nef Reaction under Oxidative Conditions. 3.1.1 Method Ox1
3.1.2 Method Ox2
3.1.3 Method Ox3
3.1.4 Method Ox4
3.1.5 Method Ox5
3.1.6 Method Ox6
3.1.7 Method Ox7
3.1.8 Method Ox8
3.1.9 Method Ox9
3.1.10 Method Ox10
3.1.11 Method Ox11
3.1.12 Method Ox12
3.1.13 Method Ox13
3.1.14 Method Ox14
3.1.15 Method Ox15
3.1.16 Method Ox16
3.1.17 Method Ox17
3.2 Nef Reaction Under Reductive Conditions. 3.2.1 Method Red1
3.2.2 Method Red2
3.2.3 Method Red3
3.2.4 Method Red4
3.3 Nef Reaction Under Basic Conditions. 3.3.1 Method Base1
3.3.2 Method Base2
3.4 Other Methods for the Nef Reaction
3.4.1 Method by NaNO2
3.4.2 Method by Me3SiCl
3.4.3 Method by SiO2/TBD
3.5 Synthetic Applications of the Nef Reaction (Representative Examples)
3.5.1 Solvolytic Methods
3.5.2 Oxidative Methods
3.5.3 Reductive Methods
3.5.4 Basic Methods
3.5.5 NaNO2 Methods
References
4 Nitroaldol (Henry) Reaction
4.1 General Catalysts and Promoters
4.1.1 Heterogeneous Catalysts and Promoters
4.1.2 Green Solvents
4.1.2.1 Nitroaldol Reaction in Water
4.1.2.2 Nitroaldol Reaction in Ionic Liquids
4.2 Nitroaldol Condensation
4.2.1 Application of General Henry Reaction
4.3 Asymmetric Henry Reaction
4.4 Aza-Henry Reaction
4.4.1 Aza-Henry Reaction via N-Protected Imines
4.4.2 Aza-Henry Reaction via α-Amidosulfones
References
5 Conjugate Addition of Nitroalkanes to Electron-Poor Alkenes (Michael Reaction)
5.1 General Homogeneous Procedures
5.2 Heterogeneous Procedures
5.3 Michael Reaction under Green Solvents
5.4 Asymmetric Michael Reaction
5.4.1 Asymmetric Michael Reaction with Enones
5.4.2 Asymmetric Michael Reaction with Enals
5.4.3 Asymmetric Michael Reaction with α,β-Unsaturated Esters
5.4.4 Asymmetric Michael Reaction with Conjugate Nitroalkenes
5.4.5 Asymmetric Michael Reaction with Vinyl Sulfones
5.5 Synthetic Applications of Michael Reaction
References
6 Formation of C—C Bond by Coupling Nitroalkanes with Aryl Halides
6.1 Main Procedures for Coupling Nitroalkanes with Aryl Halides
6.2 Application of C—C Coupling Nitroalkanes with Aryl Halides
6.3 Others
References
7 Synthesis and Reactivity of 1,3-Dinitroalkanes
7.1 Synthesis of 1,3-Dinitroalkanes
7.1.1 Asymmetric Synthesis of 1,3-Dinitroalkanes
7.1.2 Synthesis of Symmetric 1,3-Dinitroalkanes
7.2 Synthetic Applications of 1,3-Dinitroalkanes
7.2.1 Synthesis of 1,3-Diamines
7.2.2 Synthesis of Carbocycles
7.2.2.1 Synthesis of Dinitrocyclohexanols
7.2.2.2 Synthesis of Bicyclo[3.3.1]nonanes
7.2.3 Synthesis of Benzene Derivatives
7.2.3.1 Synthesis of Acetophenones and Benzoates
7.2.3.2 Synthesis of Arylamines
7.2.3.3 Synthesis of Polyfunctionalized Phenols
7.2.3.4 Synthesis of Nitrobenzenes
References
8 Formation of Carbon=Carbon Double Bonds via Nitrous Acid Elimination (NAE)
8.1 Synthesis of α,β-Unsaturated Carbonyl Derivatives
8.2 Nitroaldol Reaction, Nitrous Acid Elimination vs Water Elimination
8.3 Synthesis of Cyclic Compounds
8.3.1 Synthesis of Aromatic Rings
8.3.1.1 Synthesis of Benzene Ring
8.3.1.2 Synthesis of Furan Ring
8.3.1.3 Synthesis of Pyrrole Ring
8.3.1.4 Synthesis of Isoxazole Ring
8.3.2 Synthesis of Heterocyclic (Non-Aromatic) Rings
8.3.2.1 Synthesis of Dihydropyranol Ring
8.3.2.2 Synthesis of Butyrolactone Ring
8.3.2.3 Synthesis of Pyrrolidine Ring
8.3.2.4 Synthesis of Succinic Anhydride Ring
8.3.3 Synthesis of Cyclopentenone Ring
8.4 Synthesis of Polyenes
8.4.1 Asymmetric Synthesis of Electron-Poor Alkenes
References
9 α-Nitrocycloalkanones, Synthesis, and Reactivity
9.1 Synthesis of Cyclic α-Nitro Ketones
9.2 Ring Cleavage of Cyclic α-Nitro Ketones
9.2.1 Cleavage to ω-Nitro Acids and ω-Nitro Esters
9.2.2 Cleavage to Methyl ω-Oxoalkanoate
9.2.3 Reductive Cleavage of α-Nitrocycloalkanones
9.2.4 Oxidative Cleavage of α-Nitrocycloalkanones
9.2.4.1 Cleavage into α,ω-Dicarboxylic Acids
9.2.4.2 Cleavage to α,ω-Dicarboxylic Acids Dialkyl Esters
9.2.4.3 Cleavage to α,ω-Dicarboxylic Acids Monomethyl Esters
9.2.4.4 Cleavage to Methyl ω,ω-Dihalo-ω-nitroalkanoates
9.2.5 Reaction of α-Nitrocycloalkanones with Organometallic Reagents
9.3 α-Nitrocycloalkanones and Michael Reaction
9.4 α-Nitrocycloalkanones and Henry Reaction
9.5 “Zip Reaction”
9.5.1 Synthesis of Bicyclic Macrolactones
9.5.2 Synthesis of 12-Oxotetradecan-14-lactam
9.5.3 Asymmetric Synthesis of Bicyclic Hemiketals
9.6 Arylation of Nitrocycloalkanones
9.6.1 Synthesis of Benzo- and Naphtho-fused Bicyclo[n.3.1]structures
9.6.2 α-Arylation of 2-Nitrocycloalkanones
References
10 Acyclic α-Nitro Ketones: Synthesis and Reactivity
10.1 Synthesis of α-Nitro Ketones
10.1.1 Synthesis of α-Nitro Ketones from Henry Reaction
10.1.2 Synthesis of α-Nitro Ketones from Carboxylic Acid Derivatives
10.1.3 Synthesis of α-Nitro Ketones from Alkenes
10.1.4 Synthesis of α-Nitro Ketones from Silyl Enol Ethers
10.2 Reactivity of Acyclic α-Nitro Ketones
10.2.1 Replacement of the Nitro Group of α-Nitro Ketones
10.2.1.1 Replacement of the Nitro Group with Hydrogen
10.2.1.2 Tandem Denitration–Deoxygenation
10.2.1.3 Replacement of the Nitro Group with Deuterium
10.2.1.4 Replacement of the Nitro Group with Phenylthio Group
10.2.2 α-Nitro Ketones to Conjugated Enones
10.2.3 α-Nitro Ketones into Nitroalkanols
10.2.4 Chemoselective Reduction of α-Nitro Ketones to Amino Ketones
10.2.5 Alkylation of α-Nitro Ketones
10.2.5.1 α1-Alkylation of α-Nitro Ketones
10.2.5.2 α-Allylation of α-Nitro Ketones
10.2.5.3 α-Alkylation of α-Nitro Ketones by Michael Reaction Followed by Nitrous Acid Elimination
10.2.5.4 α-Alkylation of α-Nitro Ketones by the Mannich (or Aza-Henry) Reaction
10.3 Other Reactions
10.3.1 Synthesis of Furoxans
10.3.2 Synthesis of α-Nitro-α-Diazocarbonyl Derivatives
10.3.3 Synthesis of Acylthioamides
References
11 Nitro Cyclopropanes: Synthesis and Applications
11.1 Synthesis of Nitro Cyclopropanes
11.1.1 Synthesis of Nitro Cyclopropanes from Bromine Derivatives
11.1.2 Synthesis of Nitro Cyclopropanes from Conjugate Nitroalkenes
11.1.3 Synthesis of Nitro Cyclopropanes from Alkenes
11.1.4 Intramolecular Synthesis of Nitro Cyclopropanes from γ-Nitro Alcohols (the Mitsunobu Displacement)
11.2 Applications of Nitrocyclopropanes
11.2.1 Nitrocyclopropanes and Henry Reaction: Synthesis of Novel HIV-1 Protease Inhibitor
11.2.2 Cyclopropane Ring Expansion
References
12 Nitroalkanes as Source of Dicarbonyls
12.1 1,2-Dicarbonyl Derivatives
12.2 1,3-Dicarbonyl Derivatives
12.3 1,4-Dicarbonyl Derivatives
12.3.1 1,4-Diketones
12.3.2 γ-Ketoesters and γ-Ketoacids
12.4 1,5-Dicarbonyl Derivatives
References
13 Nitroalkanes as Source of Spiroketals
13.1 1,6-Dioxaspiro[4.4]nonanes
13.2 1,6-Dioxaspiro[4.5]undecanes
13.3 1,6-Dioxaspiro[4.6]undecanes
13.4 1,7-Dioxaspiro[5.5]undecanes and 1,7-Dioxaspiro[5.6]dodecanes
References
Index
WILEY END USER LICENSE AGREEMENT
Roberto Ballini
Alessandro Palmieri
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The procedure allows good yields with aldoximes, while fails to react with ketoximes. On the other hand, ketoximes can be converted into secondary nitroalkanes, following the Olah method [24], oxidizing ketoximes with sodium perborate in glacial acetic acid. However, this procedure failed with aldoximes.
An interesting conversion of both aldoximes and ketoximes to the corresponding nitroalkanes has been realized by a complementary synthetic route of the UHP method. In fact, the oxidation achieved with “Benz-Mo,” the Mo(VI) oxidiperoxo complex [Benz-MoO(O2)2]−(t-Bu)4N+ in acetonitrile, affords good yields of both primary and secondary nitroalkanes (Scheme 1.14) [25].
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