Roberto Ballini - Nitroalkanes

5 Chapter 5Table 5.1 Michael reaction promoted by PS-BEMP (selected examples).Table 5.2 Michael reaction of α-nitro ketones under SiO 2cat...Table 5.3 Michael reaction promoted by NaOH/CTACl system (selected examples).Table 5.4 Michael reaction performed by BmimNTf 2system (selected...

6 Chapter 6Table 6.1 Arylation of nitroalkanes minimizing their amount (selected exampl...Table 6.2 α-Arylation of secondary nitroalkanes 25into 29...

7 Chapter 7Table 7.1 Asymmetric synthesis of tetrasubstituted cyclohexanols 26.

8 Chapter 8Table 8.1 Selected examples of α,β-unsaturated carbonyls 3.

9 Chapter 9Table 9.1 Selected examples of α-nitrocycloalkanones 1.

10 Chapter 11Table 11.1 Synthesis of cyclopropanes 34.Table 11.2 Cyclopropanation of γ-nitro alcohols.

1 Introduction Figure 1 Three different typologies of nitro compounds.

2 Chapter 1 Scheme 1.1 Displacement (nitration) of alkyl halides. Scheme 1.2 Synthesis of fatty nitroalkanes. Scheme 1.3 Aryl nitromethanes synthesis under minimized purification step. Scheme 1.4 Nitration of halides with silver nitrite. Scheme 1.5 Nitration of halides with silver nitrite (selected examples). Scheme 1.6 Nitration of halides under PEG solvent. Scheme 1.7 Chemoselective nitration of alkyl halides. Scheme 1.8 Nitration of mesylates and tosylates. Scheme 1.9 Oxidation of primary amines. Scheme 1.10 Oxidation of amines using HOF·CH 3CN. Scheme 1.11 Oxidation of amines using Zr(O- t -Bu) 4. Scheme 1.12 Retro-Nef reaction via oximes. Scheme 1.13 Oxidation of oximes with TFAA/UHP. Scheme 1.14 Oxidation of oximes using Benz-Mo. Scheme 1.15 Oxidation of azides using HOF·CH 3CN. Scheme 1.16 Reduction of nitroalkenes. Scheme 1.17 Reductive nitromethylation of aldehydes. Scheme 1.18 Nitromethylation of aryl halides. Scheme 1.19 Nitroalkylation of aryl halides. Scheme 1.20 Nitroalkanes addition to vinylepoxides under Pd(0) catalysis.

3 Chapter 2 Figure 2.1 Conversion of nitroalkanes into other functionalities. Figure 2.2 Common historical procedures for the reduction of nitroalkanes to... Figure 2.3 Recent procedures for the reduction of nitroalkanes to amines.Scheme 2.1 One-pot synthesis of imines.Scheme 2.2 Synthesis of Propranolol 3.Scheme 2.3 Synthesis of threo -Dihydrosphingosine 7.Scheme 2.4 Synthesis of (−)-Denopamine 13.Scheme 2.5 Enantioselective synthesis of piperidin-2-oneScheme 2.6 Synthesis of thiourea derivative 20.Scheme 2.7 Synthesis of bicycle-γ-lactam 24.Scheme 2.8 Synthesis of ( S )-Rolipram 28.

4 Chapter 3Scheme 3.1 Nef original reaction.Scheme 3.2 Nef reaction by CAN.Scheme 3.3 Nef reaction by Fe–HCl.Figure 3.1 Intermediate of Nef reaction with basic silica gel.Scheme 3.4 Nef reaction by Me 3SiCl: synthesis of poly(1,3-diketones).Scheme 3.5 One-pot synthesis of ( R )-2-methylcyclododecanone.Scheme 3.6 One-pot synthesis of indoles 7.Scheme 3.7 One-pot synthesis of benzofurans 11.Scheme 3.8 Synthesis of Kinamycin antibiotic analogs 16.Scheme 3.9 Synthesis of γ-lactams 23.Scheme 3.10 Synthesis of sarkomycin 28.Scheme 3.11 Synthesis of (−)-Cyclophellitol 33.Scheme 3.12 Synthesis of intermediate for Manzamine A 35.Scheme 3.13 Synthesis of (−)-Pyrenophorin 41.Scheme 3.14 Synthesis of algicidal cyclopentenone 45.Scheme 3.15 Synthesis of chiral lactone 49.Scheme 3.16 Synthesis of Isosolanone 53.Scheme 3.17 Synthesis of polycyclic aromatic structure 56.Scheme 3.18 Synthesis of (−)-Botryodiplodin 60.Scheme 3.19 Synthesis of (+)-Ibuprofen 63.

5 Chapter 4Scheme 4.1 Nitroaldol (Henry) reaction.Figure 4.1 Transformation of β-nitro alcohol.Scheme 4.2 One-pot nitroaldol reaction from haloderivatives.Figure 4.2 Nitroaldol reaction vs. nitroaldol condensation.Scheme 4.3 Nitroaldol (Henry) condensation promoted by hyperbranched polyami...Scheme 4.4 Nitroaldol reaction promoted by Al 2O 3in scCO 2.Scheme 4.5 One-pot nitroaldol condensation using bromonitromethane.Scheme 4.6 Nitroaldol (Henry) reaction of BrCH 2NO 2under SmI 2catalysis.Scheme 4.7 Nitroaldol condensation by SG-MNP-NH 2.Scheme 4.8 Synthesis of A-ring of Taxane diterpene, via the Henry reaction....Scheme 4.9 Intramolecular Henry reaction with Stryker’s reagent.Scheme 4.10 Synthesis of D-Glucosamine monosaccharides.Scheme 4.11 Synthesis of ( E )-9-nitrooleic acid 17.Scheme 4.12 Synthesis of ( E )-9-nitrooleic acid 20.Scheme 4.13 Synthesis of α-Cedrene 26.Scheme 4.14 Synthesis of ( ± )-Acoradiene 32a.Scheme 4.15 Synthesis of Lycoricidine 36.Scheme 4.16 Synthesis of 4-hydroxyheptadecan-7-one 40.Scheme 4.17 Synthesis of 14-hydroxyoctadecan-8-one 44.Scheme 4.18 Synthesis of segment 48of Swinholide A.Scheme 4.19 Asymmetric Henry reaction by ligand A.Scheme 4.20 Synthesis of ( S )-Miconazole 53.Scheme 4.21 Synthesis of ( R )-Phenylephrine 57.Scheme 4.22 Synthesis of ( S )- N - trans -feruloyl 61.Scheme 4.23 Synthesis of 66.Scheme 4.24 Asymmetric synthesis of (1 R , 2 S )-methoxamine·HCl.Scheme 4.25 Asymmetric synthesis of ( S )-Toliprolol 72a, ( S )-Moprolol 72b, an...Scheme 4.26 Asymmetric synthesis of ( R )-Isoproterenol 76.Figure 4.3 Ligand G.Figure 4.4 Ligand H.Figure 4.5 Ligand I.Figure 4.6 Ligand J.Figure 4.7 Ligand K.Figure 4.8 Ligand La,b.Figure 4.9 Ligand Ma– g.Figure 4.10 Aza-Henry (or nitro-Mannich) reaction.Figure 4.11 Catalyst 134.Scheme 4.27 Asymmetric aza-Henry reaction with ligand N.Scheme 4.28 Asymmetric aza-Henry reaction with indium. Selected example.Scheme 4.29 Aza-Henry reaction of trifluoromethyl ketimines. Selected exampl...Scheme 4.30 Cyclization of 82ainto imidazoline 84.Scheme 4.31 Asymmetric aza-Henry reaction with ligand O.Scheme 4.32 Synthesis of ( S )-Levamisole 89.Scheme 4.33 Dehydrogenative aza-Henry reaction.Scheme 4.34 Three-component aza-Henry reaction via crystallization.Scheme 4.35 Reduction of amino acid. Synthesis of vicinal diamines.Scheme 4.36 Aza-Henry reaction under ligand P-Et 2Zn catalysis.Scheme 4.37 Synthesis of Epiquinamide 105.Scheme 4.38 AHR under rosin-derived amine thiourea catalyst 109and 110.Scheme 4.39 AHR under phase-transfer catalysis 113derived from cinchona alk...Scheme 4.40 Synthesis of 1,2-diamines 115and α-aminoester 117.Scheme 4.41 Asymmetric AHR catalyzed by thiourea-phosphonium salt (catalyst Scheme 4.42 Synthesis of chiral amino-substituted γ-lactam 124.Scheme 4.43 Synthesis of Taurine 129.Scheme 4.44 AHR under catalysts 130and 131.Figure 4.12 Catalyst 135.Scheme 4.45 Asymmetric synthesis of 140under catalyst 136.Scheme 4.46 Asymmetric synthesis of 145under catalyst 141.Scheme 4.47 Asymmetric synthesis of 150under catalyst 146.