Nitroalkanes

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.

• About the Authors xiiiAcknowledgments xvIntroduction xviiList of Abbreviations xix1 Synthesis of Nitroalkanes 11.1 Synthesis of Nitroalkanes 11.1.1 Displacement of Alkyl Halides 11.2 Nitration of Mesylates and Tosylates 41.3 Oxidation of Nitrogen Derivatives 51.3.1 Oxidation of Amines 51.3.2 Oxidation of Oximes 71.3.3 Oxidation of Azides 81.4 Reduction of Conjugate Nitroalkenes 81.4.1 Reduction of Nitroalkenes into Nitroalkanes 81.4.2 Stereoselective Reduction of Conjugated Nitroalkenes 101.4.3 Aldehyde Reductive Nitromethylation 101.5 Nitration of Alkanes 111.6 Metal-Catalyzed Alkylation or Arylation of Nitroalkanes 111.6.1 Nitroalkylation of Aryl Halides 121.6.2 Nitroalkylation of Allylic Esters 131.6.3 Nitroalkylation of Allylic Alcohols 131.6.4 Two-Carbon Homologation of Vinyl Triflates and Bromides 15References 162 Reduction of the Nitro Group into Amines 192.1 Representative Synthetic Applications of Nitroalkane Reductions 242.1.1 Reduction of Nitroalkanes Obtained via Nitroaldol Reaction 242.1.2 Reduction of Nitroalkanes Obtained via Michael Reaction 26References 283 Nitro Group to Carbonyl (Nef Reaction) 313.1 Nef Reaction under Oxidative Conditions 313.1.1 Method Ox1 313.1.2 Method Ox2 313.1.3 Method Ox3 323.1.4 Method Ox4 333.1.5 Method Ox5 343.1.6 Method Ox6 343.1.7 Method Ox7 343.1.8 Method Ox8 353.1.9 Method Ox9 363.1.10 Method Ox10 373.1.11 Method Ox11 373.1.12 Method Ox12 383.1.13 Method Ox13 383.1.14 Method Ox14 383.1.15 Method Ox15 393.1.16 Method Ox16 403.1.17 Method Ox17 403.2 Nef Reaction Under Reductive Conditions 413.2.1 Method Red1 413.2.2 Method Red2 423.2.3 Method Red3 433.2.4 Method Red4 433.3 Nef Reaction Under Basic Conditions 443.3.1 Method Base1 443.3.2 Method Base2 453.4 Other Methods for the Nef Reaction 463.4.1 Method by NaNO2 463.4.2 Method by Me3SiCl 473.4.3 Method by SiO2/TBD 483.5 Synthetic Applications of the Nef Reaction (Representative Examples) 493.5.1 Solvolytic Methods 493.5.2 Oxidative Methods 503.5.3 Reductive Methods 523.5.4 Basic Methods 543.5.5 NaNO2 Methods 55References 574 Nitroaldol (Henry) Reaction 594.1 General Catalysts and Promoters 604.1.1 Heterogeneous Catalysts and Promoters 604.1.2 Green Solvents 664.1.2.1 Nitroaldol Reaction inWater 674.1.2.2 Nitroaldol Reaction in Ionic Liquids 704.2 Nitroaldol Condensation 724.2.1 Application of General Henry Reaction 754.3 Asymmetric Henry Reaction 824.4 Aza-Henry Reaction 914.4.1 Aza-Henry Reaction via N-Protected Imines 924.4.2 Aza-Henry Reaction via α-Amidosulfones 96References 1025 Conjugate Addition of Nitroalkanes to Electron-Poor Alkenes (Michael Reaction) 1075.1 General Homogeneous Procedures 1075.2 Heterogeneous Procedures 1095.3 Michael Reaction under Green Solvents 1145.4 Asymmetric Michael Reaction 1175.4.1 Asymmetric Michael Reaction with Enones 1175.4.2 Asymmetric Michael Reaction with Enals 1235.4.3 Asymmetric Michael Reaction with α,β-Unsaturated Esters 1265.4.4 Asymmetric Michael Reaction with Conjugate Nitroalkenes 1265.4.5 Asymmetric Michael Reaction with Vinyl Sulfones 1285.5 Synthetic Applications of Michael Reaction 129References 1386 Formation of C—C Bond by Coupling Nitroalkanes with Aryl Halides 1416.1 Main Procedures for Coupling Nitroalkanes with Aryl Halides 1416.2 Application of C—C Coupling Nitroalkanes with Aryl Halides 1446.3 Others 147References 1497 Synthesis and Reactivity of 1,3-Dinitroalkanes 1517.1 Synthesis of 1,3-Dinitroalkanes 1517.1.1 Asymmetric Synthesis of 1,3-Dinitroalkanes 1527.1.2 Synthesis of Symmetric 1,3-Dinitroalkanes 1547.2 Synthetic Applications of 1,3-Dinitroalkanes 1567.2.1 Synthesis of 1,3-Diamines 1567.2.2 Synthesis of Carbocycles 1567.2.2.1 Synthesis of Dinitrocyclohexanols 1567.2.2.2 Synthesis of Bicyclo[3.3.1]nonanes 1577.2.3 Synthesis of Benzene Derivatives 1597.2.3.1 Synthesis of Acetophenones and Benzoates 1597.2.3.2 Synthesis of Arylamines 1617.2.3.3 Synthesis of Polyfunctionalized Phenols 1617.2.3.4 Synthesis of Nitrobenzenes 162References 1638 Formation of Carbon=Carbon Double Bonds via Nitrous Acid Elimination (NAE) 1658.1 Synthesis of α,β-Unsaturated Carbonyl Derivatives 1658.2 Nitroaldol Reaction, Nitrous Acid Elimination vs Water Elimination 1708.3 Synthesis of Cyclic Compounds 1718.3.1 Synthesis of Aromatic Rings 1718.3.1.1 Synthesis of Benzene Ring 1718.3.1.2 Synthesis of Furan Ring 1748.3.1.3 Synthesis of Pyrrole Ring 1768.3.1.4 Synthesis of Isoxazole Ring 1768.3.2 Synthesis of Heterocyclic (Non-Aromatic) Rings 1768.3.2.1 Synthesis of Dihydropyranol Ring 1778.3.2.2 Synthesis of Butyrolactone Ring 1778.3.2.3 Synthesis of Pyrrolidine Ring 1788.3.2.4 Synthesis of Succinic Anhydride Ring 1788.3.3 Synthesis of Cyclopentenone Ring 1798.4 Synthesis of Polyenes 1808.4.1 Asymmetric Synthesis of Electron-Poor Alkenes 183References 1859 ;;-Nitrocycloalkanones, Synthesis, and Reactivity 1879.1 Synthesis of Cyclic α-Nitro Ketones 1879.2 Ring Cleavage of Cyclic α-Nitro Ketones 1899.2.1 Cleavage to ω-Nitro Acids and ω-Nitro Esters 1909.2.2 Cleavage to Methyl ω-Oxoalkanoate 1929.2.3 Reductive Cleavage of α-Nitrocycloalkanones 1939.2.4 Oxidative Cleavage of α-Nitrocycloalkanones 1939.2.4.1 Cleavage into α,ω-Dicarboxylic Acids 1939.2.4.2 Cleavage to α,ω-Dicarboxylic Acids Dialkyl Esters 1959.2.4.3 Cleavage to α,ω-Dicarboxylic Acids Monomethyl Esters 1959.2.4.4 Cleavage to Methyl ω,ω-Dihalo-ω-nitroalkanoates 1969.2.5 Reaction of α-Nitrocycloalkanones with Organometallic Reagents 1969.3 α-Nitrocycloalkanones and Michael Reaction 1989.4 α-Nitrocycloalkanones and Henry Reaction 2009.5 “Zip Reaction” 2019.5.1 Synthesis of Bicyclic Macrolactones 2029.5.2 Synthesis of 12-Oxotetradecan-14-lactam 2029.5.3 Asymmetric Synthesis of Bicyclic Hemiketals 2039.6 Arylation of Nitrocycloalkanones 2039.6.1 Synthesis of Benzo- and Naphtho-fused Bicyclo[n.3.1]structures 2049.6.2 α-Arylation of 2-Nitrocycloalkanones 205References 20610 Acyclic ;;-Nitro Ketones: Synthesis and Reactivity 20910.1 Synthesis of α-Nitro Ketones 20910.1.1 Synthesis of α-Nitro Ketones from Henry Reaction 20910.1.2 Synthesis of α-Nitro Ketones from Carboxylic Acid Derivatives 21110.1.3 Synthesis of α-Nitro Ketones from Alkenes 21210.1.4 Synthesis of α-Nitro Ketones from Silyl Enol Ethers 21210.2 Reactivity of Acyclic α-Nitro Ketones 21310.2.1 Replacement of the Nitro Group of α-Nitro Ketones 21310.2.1.1 Replacement of the Nitro Group with Hydrogen 21310.2.1.2 Tandem Denitration–Deoxygenation 21710.2.1.3 Replacement of the Nitro Group with Deuterium 22010.2.1.4 Replacement of the Nitro Group with Phenylthio Group 22110.2.2 α-Nitro Ketones to Conjugated Enones 22110.2.3 α-Nitro Ketones into Nitroalkanols 22410.2.4 Chemoselective Reduction of α-Nitro Ketones to Amino Ketones 22610.2.5 Alkylation of α-Nitro Ketones 22810.2.5.1 α1-Alkylation of α-Nitro Ketones 22810.2.5.2 α-Allylation of α-Nitro Ketones 22910.2.5.3 α-Alkylation of α-Nitro Ketones by Michael Reaction Followed by Nitrous Acid Elimination 23210.2.5.4 α-Alkylation of α-Nitro Ketones by the Mannich (or Aza-Henry) Reaction 23510.3 Other Reactions 23510.3.1 Synthesis of Furoxans 23510.3.2 Synthesis of α-Nitro-α-Diazocarbonyl Derivatives 23610.3.3 Synthesis of Acylthioamides 236References 23711 Nitro Cyclopropanes: Synthesis and Applications 23911.1 Synthesis of Nitro Cyclopropanes 23911.1.1 Synthesis of Nitro Cyclopropanes from Bromine Derivatives 23911.1.2 Synthesis of Nitro Cyclopropanes from Conjugate Nitroalkenes 24711.1.3 Synthesis of Nitro Cyclopropanes from Alkenes 25011.1.4 Intramolecular Synthesis of Nitro Cyclopropanes from γ-Nitro Alcohols (the Mitsunobu Displacement) 25311.2 Applications of Nitrocyclopropanes 25611.2.1 Nitrocyclopropanes and Henry Reaction: Synthesis of Novel HIV-1 Protease Inhibitor. 25611.2.2 Cyclopropane Ring Expansion 257References 26112 Nitroalkanes as Source of Dicarbonyls 26312.1 1,2-Dicarbonyl Derivatives 26312.2 1,3-Dicarbonyl Derivatives 26512.3 1,4-Dicarbonyl Derivatives 26612.3.1 1,4-Diketones 26612.3.2 γ-Ketoesters and γ-Ketoacids 27212.4 1,5-Dicarbonyl Derivatives 275References 27613 Nitroalkanes as Source of Spiroketals 27713.1 1,6-Dioxaspiro[4.4]nonanes 27713.2 1,6-Dioxaspiro[4.5]undecanes 27913.3 1,6-Dioxaspiro[4.6]undecanes 28113.4 1,7-Dioxaspiro[5.5]undecanes and 1,7-Dioxaspiro[5.6]dodecanes 283References 284Index 285

Select Guide Rating