Nitroalkanes. Roberto Ballini

5.19 Michael reaction catalyzed by diamine 52.Scheme 5.20 Conjugate addition of prochiral nitroalkanes to acrylate equival...Scheme 5.21 Synthesis of (S)- and (R)-Baclofen 60a,b.Figure 5.5 Possible adducts (ways a–c) of nitroalkanes to enals.Scheme 5.22 Asymmetric Michael reaction promoted by the organocatalyst 62.Scheme 5.23 Asymmetric synthesis of (R)-Baclofen·HCl salt 64.Scheme 5.24 Asymmetric Michael reaction promoted by catalyst 65 under aqueou...Scheme 5.25 Synthesis of (S)-Rolipram 69.Scheme 5.26 Synthesis of Pregabalin 73.Scheme 5.27 Michael reaction promoted by the catalyst 74.Scheme 5.28 Michael reaction promoted by the catalyst 62.Scheme 5.29 Synthetic applications of compound 77a (R = Ph).Scheme 5.30 Intramolecular reaction promoted by the catalyst 84.Scheme 5.31 Asymmetric Michael reaction with nitroalkenes promoted by the ca...Scheme 5.32 Asymmetric Michael reaction with nitroalkenes promoted by the ca...Scheme 5.33 Asymmetric Michael reaction with vinyl sulfone promoted by the c...Scheme 5.34 Synthesis of 2,3,4-tetrahydroisoquinoline 102.Scheme 5.35 Synthesis of (±)-Norsalanadione 105.Figure 5.6 Taxol.Scheme 5.36 Synthesis of A ring of Taxol 111.Scheme 5.37 Synthesis of (+)-Trachelanthamidin 117.Scheme 5.38 Synthesis of Isolactone 122.Scheme 5.39 Synthesis of (−)-δ-Multistriatin pheromone 127.Scheme 5.40 Synthesis of bicyclic-γ-lactam proteins 131.Scheme 5.41 Synthesis of (R)-Palulolide A 135.Scheme 5.42 Synthesis of (3S,4R)-Paroxetine A 140.Scheme 5.43 Synthesis of Trandolapril 147.Scheme 5.44 Synthesis of (−)-Epibatidine 152.Scheme 5.45 Synthesis of (±)-Manzacidin A and C.Scheme 5.46 Synthesis of Dipeptidyl peptidase IV inhibitor 165.

      7 Chapter 6Figure 6.1 Pioneering coupling reactions.Scheme 6.1 Coupling of aryl halides 1 with nitroalkanes 2.Scheme 6.2 Synthesis of NH-9.Scheme 6.3 α-Arylation of aryl nitromethanes 7.Scheme 6.4 α-One-pot diarylation of nitromethane.Figure 6.2 Arylation of nitroalkanes in water.Scheme 6.5 Orthogonal formylation equivalent of aryl halides/triflates 1–13....Scheme 6.6 Synthesis of 3-alkyl-2-isoxazolines 17.Scheme 6.7 One-pot synthesis of 1H-2,3-benzoxazine-3-oxide 20.Scheme 6.8 Synthesis of 5-alkyl-5-aryl-1-pyrroline N-oxides (AAPOs) 22.Scheme 6.9 Synthesis of γ-lactams 24.Scheme 6.10 Trifluoromethylation of secondary nitroalkanes into 27.Scheme 6.11 Synthesis of (±)-Adalinine 34.

      8 Chapter 7Scheme 7.1 1,3-Dinitroalkanes transformations.Scheme 7.2 Synthesis of 1,3-dinitroalkanes (pathway a or b).Scheme 7.3 Asymmetric conjugate addition of nitroalkanes to nitroalkenes.Scheme 7.4 Asymmetric conjugate addition of silyl nitronates promoted by the...Scheme 7.5 Electrochemical synthesis of 1,3-dinitroalkanes.Scheme 7.6 Synthesis of 1,3-dinitroalkanes promoted by basic Al₂O₃.Scheme 7.7 Synthesis of 1,3-dinitroalkanes under Ni-species.Scheme 7.8 Synthesis of linear 1,3-dinitroalkanes 20.Scheme 7.9 Reduction of chiral 1,3-dinitroalkanes to 1,3-diamines 22.Scheme 7.10 One-pot synthesis of 2,4-dinitrocyclohexanols 24.Scheme 7.11 One-pot synthesis of bicyclo[3.3.1]nonanes 29.Scheme 7.12 One-pot synthesis of bis-bicyclic compounds 31.Scheme 7.13 One-pot synthesis of benzoyl derivatives 36.Scheme 7.14 One-pot synthesis of 38.Scheme 7.15 Synthesis of diarylamines 41.Scheme 7.16 Synthesis of phenols 43.Scheme 7.17 Synthesis of phenols 46 and 47.Scheme 7.18 Synthesis of phenols 50.

      9 Chapter 8Figure 8.1 Base-induced elimination of nitrous acid.Scheme 8.1 Synthesis of α,β-unsaturated carbonyl derivatives 3.Figure 8.2 Nitroalkane as synthetic equivalent of the alkyl anion synthon I....Scheme 8.2 Synthesis of succinate derivatives 4a and N-ethylsuccinimmides 4dScheme 8.3 Chemoselective formation of adducts 6 or 7.Scheme 8.4 Chemoselective one-pot formation of adducts 10.Scheme 8.5 One-pot formation of tetrahydrofuran 12.Scheme 8.6 Reduction of 10 into triols 13.Scheme 8.7 Synthesis of α,β-unsaturated esters 16.Scheme 8.8 Synthesis of nitro-functionalized α,β-unsaturated esters 18 and 1...Scheme 8.9 Synthesis of enediones 23.Scheme 8.10 Synthesis of ketones 27 via HNO₂ elimination vs. H₂O.Scheme 8.11 Synthesis of acetophenones 33.Scheme 8.12 Synthesis of carbazoles 36.Scheme 8.13 Synthesis of naphthyl derivatives 40.Scheme 8.14 Synthesis of tetrasubstituted benzenes 45.Scheme 8.15 Synthesis of trisubstituted furans 50.Figure 8.3 Nitroalkane as synthetic equivalent of the alkyl cation synthon I...Scheme 8.16 Synthesis of disubstituted furans 57.Scheme 8.17 Synthesis of furan ring YC-1.Scheme 8.18 Synthesis of pyrroles 67.Scheme 8.19 Synthesis of isoxazoles 74.Scheme 8.20 Synthesis of dihydropyranols 78.Scheme 8.21 Synthesis of butyrolactones 82.Scheme 8.22 Synthesis of α-methylene-γ-butyrolactones 84 and 85.Scheme 8.23 Synthesis of pyrrolidines 86.Scheme 8.24 Synthesis of succinic anhydrides 88 and 91.Scheme 8.25 Synthesis of cyclopentenones 96.Scheme 8.26 Synthesis of 1,3-diene-tricarboxylates 99.Scheme 8.27 Synthesis of 1,3-butadienes 100.Scheme 8.28 Synthesis of nitrodiesters 102 or 1,3-butadienes 103.Scheme 8.29 Synthesis of γ-lactams 105 and 106.Scheme 8.30 Asymmetric synthesis of conjugate alkenes 111 and their applicat...Scheme 8.31 Asymmetric one-pot vinylation of enals 114.Figure 8.4 Nitroalkanes 107a as synthetic equivalent of the vinyl anion synt...

      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 9 and 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 9 by CTACl.Scheme 9.6 Synthesis of ω-aminoacids 14.Scheme 9.7 Synthesis of keto ester 18 and 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 30a and 30b.Scheme 9.11 Synthesis of α,ω-dicarboxylic acids 33 and 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 60 and 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 89 and 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 4a via the Henry reaction.Scheme 10.2 One-pot