Nitroalkanes. Roberto Ballini

10.3 Synthesis of α-nitro ketones 4c from phenylselenyl acetaldehyde Scheme 10.4 Synthesis of α-nitro ketones 4a–c from acylimidazoles 9.Scheme 10.5 Synthesis of α-nitro ketones 4c from acylchloride 10.Scheme 10.6 Synthesis of α-nitro ketones 4b from alkenes 13.Scheme 10.7 Synthesis of α-nitro ketones 4d form nitroalkenes 15.Scheme 10.8 Synthesis of α-nitro ketones 4a from silyl enol ether 16.Scheme 10.9 Denitration of α-nitro ketones 4b by Bu₃SnH.Scheme 10.10 Denitration of α-nitro ketones 4a by Na₂S₂O₄.Scheme 10.11 Denitration of α-nitro ketones 4c into 21.Scheme 10.12 Denitration of α-nitro ketones 4a into 25.Scheme 10.13 Synthesis of (Z)-5-undecen-2-one 30.Scheme 10.14 Synthesis of methyl 9-oxodecanoate 35a and methyl 9-oxo-12-trid...Scheme 10.15 Synthesis of (Z)-heneicos-6-en-11-one 41.Figure 10.1 Nitroalkenes 26, 31, and 36 as synthetic equivalents of carbanio...Scheme 10.16 Denitration–deoxygenation of α-nitro ketones using LiAlH₄.Scheme 10.17 Synthesis of (Z)-9-tricosene 47.Scheme 10.18 Denitration–deoxygenation of α-nitro ketones using NaBH₄.Scheme 10.19 Synthesis of 2-methylheptadecane 52.Figure 10.2 Nitroalkanes 44 and 49 as synthetic equivalents of carbanion syn...Scheme 10.20 Synthesis of α-deuterated ketones 53–55.Scheme 10.21 Deuteration of α-nitro ketones via tosylhydrazones.Scheme 10.22 Replacement of nitro group with “SPh.”Scheme 10.23 Synthesis of conjugate enones 63.Scheme 10.24 α-Nitro ketones into enones 67 via tosylhydrazones.Scheme 10.25 Regioselective formation of α,β-unsaturated ketones 72 and 77....Scheme 10.26 Synthesis of (E)-2-ene-1,4-diones 81.Scheme 10.27 Asymmetric reduction of α-nitro ketones to nitroalkanols 82.Scheme 10.28 Symmetric reduction of α-nitro ketones 4a to nitroalkanols 84....Scheme 10.29 Asymmetric reduction of α-nitro acetophenones 85 into nitroalka...Figure 10.3 α-Acidic proton of α-nitro ketones 4b,c.Scheme 10.30 Asymmetric nucleophilic addition of R²Li to α-nitro ketones 4b ...Scheme 10.31 Chemoselective reduction of the nitro group of α-nitro ketones Scheme 10.32 Synthesis of 94.Scheme 10.33 Synthesis of 5-ALA 88.Scheme 10.34 Synthesis of trialkyl-substituted pyrazines 100.Figure 10.4 α-Nitro ketones: main three centers prone to form C—C bond.Scheme 10.35 α¹-Alkylation of α-nitro ketones.Scheme 10.36 Synthesis of (±)-Muscone 107.Scheme 10.37 α-Alkylation of α-nitro ketones 4b into 109 and 110.Scheme 10.38 Mono-allylation of nitroacetone derivatives via deacylation of Scheme 10.39 Unsymmetric bis-allylation of nitroalkanes 116 from α-nitro ket...Scheme 10.40 Tris-allylation of nitro ketone 4c.Scheme 10.41 Allylation of 1,4-dienes by C–H activation of α-nitr...Scheme 10.42 One-pot synthesis of α,β-unsaturated hydrazones 123.Scheme 10.43 Synthesis of 2,3-dihydrofurans 126.Scheme 10.44 Synthesis of dihydrofurans 130.Scheme 10.45 Synthesis of furans 134.Scheme 10.46 Synthesis of trisubstituted isoxazoles 138.Scheme 10.47 Synthesis of α-pyrones 143.Scheme 10.48 Alkylation of 4b,c by nitro-Mannich and Mannich-type reactions....Scheme 10.49 Synthesis of furoxans 148.Scheme 10.50 Synthesis of α-nitro-α-diazocarbonyls 149.Scheme 10.51 Synthesis of acylthioamides 150 and acylthioureas 151.

      12 Chapter 11Figure 11.1 Hormaomycin (A).Figure 11.2 Synthetic applications of nitrocyclopropanes.Scheme 11.1 Nitrocyclopropanation of γ-nitro ketones 1.Scheme 11.2 Nitrocyclopropanation of steroids 4.Scheme 11.3 Nitrocyclopropanation of 7 into 10.Scheme 11.4 Nitrocyclopropanation of 11a into 14a.Scheme 11.5 Synthesis of unit 18, key constituent of Belactosin A 19.Scheme 11.6 Synthesis of 22.Scheme 11.7 Cyclopropanation of 23.Scheme 11.8 Cyclopropanation of 23 into 28.Scheme 11.9 Cyclopropanation of 30a into 31a.Scheme 11.10 Synthesis of Trovafloxacin 32.Scheme 11.11 Cyclopropanation of 33.Scheme 11.12 Cyclopropanation of 30a–d under K₂CO₃ catalysis.Scheme 11.13 Cyclopropanation of 35 into 37 under K₂CO₃ catalysis.Figure 11.3 Push–pull effect.Scheme 11.14 Preparation of CF₃-amino acid 41.Scheme 11.15 Synthesis of CF₃-peptide 45.Scheme 11.16 Synthesis of nitro cyclopropanes 49.Scheme 11.17 Cyclopropanation of nitroalkanes 50 into 52.Scheme 11.18 Cyclopropanation of nitroalkenes 53 into 56.Scheme 11.19 Cyclopropanation of nitroalkenes 53 into 58.Scheme 11.20 Cyclopropanation of nitroalkenes 53 into 60.Scheme 11.21 Synthesis of CBB3001 65.Figure 11.4 Preparation of nitrodiazo compounds 66.Scheme 11.22 Nitration of diazo compounds into 66.Scheme 11.23 Cyclopropanation of 66 into 67.Scheme 11.24 Decarboxylation of 67a into nitrocyclopropanes 69 and cycloprop...Scheme 11.25 Double ways (A and B) to obtain cyclopropyl amines 74.Scheme 11.26 Asymmetric cyclopropanation of alkenes 71a into 76.Figure 11.5 Organocatalyst 78.Scheme 11.27 Trans–cis isomerization of 76.Scheme 11.28 Synthesis of subunits 87 and 88.Figure 11.6 Hormaomycin (A), Belactosin A (D), and their subunits (NcP)Ala 8...Figure 11.7 Cyclopropanation of γ-nitroalcohols.Scheme 11.29 Synthesis of 95.Scheme 11.30 Synthesis of novel HIV-1 protease inhibitors 101a,b.Scheme 11.31 Tandem ring opening/cyclization of cyclopropanes 102 into 104....Scheme 11.32 Mechanism for the formation of 104.Scheme 11.33 [3+2]-Cycloaddition of nitrocyclopropanes 105 with styrenes 106Scheme 11.34 Intramolecular reaction of nitrocyclopropanes 108 into digydrof...Scheme 11.35 Synthesis of dihydrofurans 111. Selected examplesScheme 11.36 Synthesis of cyclopentenes 112. Selected examples.

      13 Chapter 12Scheme 12.1 Synthesis of α-ketoacids 2.Figure 12.1 1,n-Dicarbonyls.Scheme 12.2 Synthesis of 1,2-dicarbonyls 8.Figure 12.2 Synthetic equivalents of 3 and 4.Scheme 12.3 Synthesis of β-ketoesters 12.Scheme 12.4 Synthesis of 1,3-diketones 16.Scheme 12.5 Synthesis of β-ketoesters 20.Scheme 12.6 Synthesis of 1,4-diketones 24.Scheme 12.7 One-pot synthesis of 1,4-diketones 27.Scheme 12.8 One-pot synthesis of 1,4,7-triketones 29.Scheme 12.9 One-pot synthesis of 1,4-diketones 31.Scheme 12.10 One-pot synthesis of 1,4-diketones 35.Scheme 12.11 One-pot synthesis of (E)-alylidene-1,4-diones 38.Scheme 12.12 One-pot synthesis of 1,4-diketones 42a or γ-ketoaldehydes 42b....Scheme 12.13 One-pot synthesis of (E)-enediones 46.Scheme 12.14 Synthesis of 1,4-dione 50, precursor of ketoprofen 51.Scheme 12.15 Synthesis of cyclopentenone 55, precursor of Cuparene 56.Scheme 12.16 One-pot synthesis of Allylrethrone 59.Scheme 12.17 Synthesis of (Z)-Jasmone 62b and methyl Jasmonate 63.Scheme 12.18 Synthesis of γ-ketoesters 66 or γ-ketoacids 67.Scheme 12.19 Synthesis of (R)-(+)-γ-caprolactone.Scheme 12.20 Synthesis of γ-ketoesters 69 via Michael reaction.Scheme 12.21 One-pot synthesis of γ-ketodiesters 72.Scheme 12.22 One-pot synthesis of γ-ketodiesters 75.Scheme 12.23 Synthesis of exo-methylene butyrolactones 79.Scheme 12.24 Synthesis of γ-ketoacids 81 or γ-ketoaldehydes 83.Scheme 12.25 Synthesis of γ-keto α,β-unsaturated esters 86.Scheme 12.26 Synthesis of 1,5-diketones 91.Scheme