Roberto Ballini - Nitroalkanes

10 Chapter 9Figure 9.1 Synthesis of α-nitrocycloalkanones 1.Scheme 9.1 Synthesis of steroid α-nitro ketones 6a–d.Figure 9.2 Ring cleavage of α-nitrocycloalkanones.Scheme 9.2 Synthesis of ω-nitro acids 9and ω-nitro esters 10.Scheme 9.3 Cleavage of nitro cycloalkanones with MeOH/Amberlyst A21.Scheme 9.4 Synthesis of Exaltolide 13.Scheme 9.5 Ring cleavage to ω-nitro acids 9by CTACl.Scheme 9.6 Synthesis of ω-aminoacids 14.Scheme 9.7 Synthesis of keto ester 18and keto acid 19.Scheme 9.8 Synthesis of methyl ω-oxoalkanoates 21.Scheme 9.9 Synthesis of ω-nitroalcohols 22.Scheme 9.10 Synthesis of ( R )-Patulolide A and B 30aand 30b.Scheme 9.11 Synthesis of α,ω-dicarboxylic acids 33and keto acids 32.Scheme 9.12 Synthesis of α,ω-dicarboxylic acids dialkyl esters 34.Scheme 9.13 Ring cleavage of steroid nitro ketone 35.Scheme 9.14 Oxidative cleavage of 2-nitro cycloalkanones by Oxone®.Scheme 9.15 Oxidative cleavage of 2-nitro cycloalkanones by NaClO into 39.Scheme 9.16 Nucleophilic addition of Grignard reagents to α-nitrocyclohexano...Scheme 9.17 Synthesis of (±)-Phoracantholide 45.Scheme 9.18 Synthesis of ( R )-(+)-α-Lipoic acid 48.Figure 9.3 Acidity of hydrogen in 2-position.Scheme 9.19 Synthesis of nitrocyclohexenes 50.Scheme 9.20 Asymmetric Michael reaction of 2-nitrocyclohexanone to nitroalke...Scheme 9.21 Asymmetric synthesis of 1-azaspiro[4.5]decan-6-one 57.Scheme 9.22 Asymmetric synthesis of bicyclic 60and macrocyclic 63.Scheme 9.23 Synthesis of ( E )-12-nitrooctadecadec-12-enoic acid methyl ester Scheme 9.24 Synthesis of Indane derivatives 72.Figure 9.4 Zip reactions.Scheme 9.25 Synthesis of functionalized macrolactones 80.Scheme 9.26 Synthesis of functionalized macrolactam 85.Scheme 9.27 Asymmetric synthesis of bicyclic skeleton 89and ring cleavage t...Scheme 9.28 Synthesis of benzo- and naphtho-fused bicyclo[ n .3.1]structure 93Scheme 9.29 Synthesis of bridget 2,8-dioxabicylclo[3.2.1]octanes 95.Scheme 9.30 Synthesis of tertiary α-aryl-α-nitrocycloalkanone 97.Scheme 9.31 Synthesis of Tiletamine 100.

11 Chapter 10Scheme 10.1 Synthesis of α-nitro ketones 4avia the Henry reaction.Scheme 10.2 One-pot synthesis of α-nitro ketones 4avia the Henry reaction....Scheme 10.3 Synthesis of α-nitro ketones 4cfrom phenylselenyl acetaldehyde Scheme 10.4 Synthesis of α-nitro ketones 4a–cfrom acylimidazoles 9.Scheme 10.5 Synthesis of α-nitro ketones 4cfrom acylchloride 10.Scheme 10.6 Synthesis of α-nitro ketones 4bfrom alkenes 13.Scheme 10.7 Synthesis of α-nitro ketones 4dform nitroalkenes 15.Scheme 10.8 Synthesis of α-nitro ketones 4afrom silyl enol ether 16.Scheme 10.9 Denitration of α-nitro ketones 4bby Bu 3SnH.Scheme 10.10 Denitration of α-nitro ketones 4aby Na 2S 2O 4.Scheme 10.11 Denitration of α-nitro ketones 4cinto 21.Scheme 10.12 Denitration of α-nitro ketones 4ainto 25.Scheme 10.13 Synthesis of ( Z )-5-undecen-2-one 30.Scheme 10.14 Synthesis of methyl 9-oxodecanoate 35aand methyl 9-oxo-12-trid...Scheme 10.15 Synthesis of ( Z )-heneicos-6-en-11-one 41.Figure 10.1 Nitroalkenes 26, 31, and 36as synthetic equivalents of carbanio...Scheme 10.16 Denitration–deoxygenation of α-nitro ketones using LiAlH 4.Scheme 10.17 Synthesis of ( Z )-9-tricosene 47.Scheme 10.18 Denitration–deoxygenation of α-nitro ketones using NaBH 4.Scheme 10.19 Synthesis of 2-methylheptadecane 52.Figure 10.2 Nitroalkanes 44and 49as 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 67via tosylhydrazones.Scheme 10.25 Regioselective formation of α,β-unsaturated ketones 72and 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 4ato nitroalkanols 84....Scheme 10.29 Asymmetric reduction of α-nitro acetophenones 85into nitroalka...Figure 10.3 α-Acidic proton of α-nitro ketones 4b,c.Scheme 10.30 Asymmetric nucleophilic addition of R 2Li 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 α 1-Alkylation of α-nitro ketones.Scheme 10.36 Synthesis of (±)-Muscone 107.Scheme 10.37 α-Alkylation of α-nitro ketones 4binto 109and 110.Scheme 10.38 Mono-allylation of nitroacetone derivatives via deacylation of Scheme 10.39 Unsymmetric bis-allylation of nitroalkanes 116from 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,cby 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 150and 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 7into 10.Scheme 11.4 Nitrocyclopropanation of 11ainto 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 23into 28.Scheme 11.9 Cyclopropanation of 30ainto 31a.Scheme 11.10 Synthesis of Trovafloxacin 32.Scheme 11.11 Cyclopropanation of 33.Scheme 11.12 Cyclopropanation of 30a–dunder K 2CO 3catalysis.Scheme 11.13 Cyclopropanation of 35into 37under K 2CO 3catalysis.Figure 11.3 Push–pull effect.Scheme 11.14 Preparation of CF 3-amino acid 41.Scheme 11.15 Synthesis of CF 3-peptide 45.Scheme 11.16 Synthesis of nitro cyclopropanes 49.Scheme 11.17 Cyclopropanation of nitroalkanes 50into 52.Scheme 11.18 Cyclopropanation of nitroalkenes 53into 56.Scheme 11.19 Cyclopropanation of nitroalkenes 53into 58.Scheme 11.20 Cyclopropanation of nitroalkenes 53into 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 66into 67.Scheme 11.24 Decarboxylation of 67ainto nitrocyclopropanes 69and cycloprop...Scheme 11.25 Double ways ( Aand B) to obtain cyclopropyl amines 74.Scheme 11.26 Asymmetric cyclopropanation of alkenes 71ainto 76.Figure 11.5 Organocatalyst 78.Scheme 11.27 Trans – cis isomerization of 76.Scheme 11.28 Synthesis of subunits 87and 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 102into 104....Scheme 11.32 Mechanism for the formation of 104.Scheme 11.33 [3+2]-Cycloaddition of nitrocyclopropanes 105with styrenes 106Scheme 11.34 Intramolecular reaction of nitrocyclopropanes 108into digydrof...Scheme 11.35 Synthesis of dihydrofurans 111. Selected examplesScheme 11.36 Synthesis of cyclopentenes 112. Selected examples.