Roberto Ballini - Nitroalkanes

6 Chapter 5Figure 5.1 Conjugate addition (Michael reaction).Scheme 5.1 Synthesis of diamino alcohols 4from in situ Henry–Michael reacti...Scheme 5.2 Synthesis of methylene butyrolactones 8.Scheme 5.3 Synthesis of α,β-unsaturated nitriles 12.Scheme 5.4 Michael reaction using Amberlyst A27 as promoter.Scheme 5.5 Michael reaction using Isolute® as promoter.Figure 5.2 Structure of PS-BEMP.Scheme 5.6 One-pot Henry–Michael reaction promoted by Isolute®.Scheme 5.7 Intramolecular Michael reaction.Scheme 5.8 One-pot Michael reaction from haloderivatives.Scheme 5.9 Conjugate addition to the dienoic ester 23.Scheme 5.10 One-pot synthesis of 1,4-difuntionalized molecules from nitroalk...Scheme 5.11 Synthesis of substituted Δ 1-pyrrolines 33.Scheme 5.12 Michael reaction of nitroalkanes under chiral imidazoline–tetraz...Scheme 5.13 Michael reaction of nitroalkanes under 5-pyrrolidin-2-yltetrazol...Scheme 5.14 Michael reaction of nitroalkanes catalyzed by trans -amino-prolin...Figure 5.3 α-Aminophosphonate.Scheme 5.15 Michael reaction of nitroalkanes catalyzed by Cinchona alkaloid ...Figure 5.4 Catalyst 44.Scheme 5.16 Michael reaction catalyzed by the thiourea 45.Scheme 5.17 Conjugate addition of α-nitroacetate to α,β-unsaturated ketones ...Scheme 5.18 Synthetic applications of 49.Scheme 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 65under 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 Aring 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 (3 S ,4 R )-Paroxetine A 140.Scheme 5.43 Synthesis of Trandolapril 147.Scheme 5.44 Synthesis of (−)-Epibatidine 152.Scheme 5.45 Synthesis of (±)-Manzacidin Aand 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 1with 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 1 H -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 Al 2O 3.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 46and 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 4aand N -ethylsuccinimmides 4dScheme 8.3 Chemoselective formation of adducts 6or 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 10into triols 13.Scheme 8.7 Synthesis of α,β-unsaturated esters 16.Scheme 8.8 Synthesis of nitro-functionalized α,β-unsaturated esters 18and 1...Scheme 8.9 Synthesis of enediones 23.Scheme 8.10 Synthesis of ketones 27via HNO 2elimination vs. H 2O.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 84and 85.Scheme 8.23 Synthesis of pyrrolidines 86.Scheme 8.24 Synthesis of succinic anhydrides 88and 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 102or 1,3-butadienes 103.Scheme 8.29 Synthesis of γ-lactams 105and 106.Scheme 8.30 Asymmetric synthesis of conjugate alkenes 111and their applicat...Scheme 8.31 Asymmetric one-pot vinylation of enals 114.Figure 8.4 Nitroalkanes 107aas synthetic equivalent of the vinyl anion synt...