Non-Conventional Solvents. Volume 2: Organic Synthesis, Natural Products Isolation, Drug Design, Industry and the Environment

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Also of Interest
Non-Conventional Solvents. Volume 2: Organic Synthesis, Natural Products Isolation, Drug Design, Industry and the Environment
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Foreword
About Professor Bimal Krishna Banik
Contents
List of contributors
1. Triethylamine-mediated synthesis of bioactive heterocycles
	1.1 Introduction
	1.2 Triethylamine-promoted photocatalytic reactions
		1.2.1 Photocatalytic triethylamine-mediated synthesis of 1,4-substituted 1,2,3-triazoles
		1.2.2 Reductive alkylation of difluoroalkyl halides using triethylamine as reductant
		1.2.3 Triethylamine-mediated aerobic oxidation of sulfides
		1.2.4 Photocatalytic triethylamine-mediated synthesis of 6-β-disubstituted phenanthridines
		1.2.5 Photocatalytic triethylamine-mediated synthesis of C3-alkylated imidazopyridines
		1.2.6 Visible-light-driven triethylamine-mediated photocatalytic duet reaction
		1.2.7 Photocatalytic triethylamine-mediated synthesis of phenols
		1.2.8 Photocatalytic triethylamine-mediated synthesis of indoline
		1.2.9 Photocatalytic triethylamine-mediated oxidation of alcohols
	1.3 Triethylamine-promoted electrochemical reactions
		1.3.1 Triethylamine-mediated electrochemical alcohol oxidation
		1.3.2 Triethylamine-mediated electrochemical reductive decarboxylative coupling
		1.3.3 Triethylamine-mediated electrocatalyzed mild C–H alkylations
	1.4 Triethylamine-promoted organic reactions
		1.4.1 Triethylamine-mediated synthesis of 2-oxazolidinones
		1.4.2 Triethylamine-mediated synthesis of dialkyl 2-thiofumarates
		1.4.3 Selective synthesis of multifunctionalized cyclopent-3-ene-1-carboxamides and 2-oxabicyclo[2.2.1]heptane derivatives
		1.4.4 Triethylamine-mediated Knoevenagel condensation
		1.4.5 Triethylamine-mediated synthesis of phosphonate diols
		1.4.6 Triethylamine-mediated regioselective synthesis of the indolopyrazines
	1.5 Conclusions
	References
2. Organic transformations in nitromethane as solvent
	2.1 Introduction
	2.2 C–C bond formation in nitromethane
		2.2.1 Alkylation of 1,3-dicarbonyl compounds
		2.2.2 Benzylation of 1,3-dicarbonyl compounds
		2.2.3 Friedel–Crafts alkylation of indoles
		2.2.4 Friedel–Crafts alkylation of biaryl alcohols
		2.2.5 Alkylation of various arenes
		2.2.6 Tsuji–Trost coupling reaction
		2.2.7 Intramolecular Friedel–Crafts reaction
		2.2.8 Synthesis of 1,4-diynes
		2.2.9 Synthesis of tetra-aryl-substituted cyclopentenes
		2.2.10 Synthesis of substituted aryl ketones
		2.2.11 Synthesis of trisubstituted alkenes
		2.2.12 Synthesis of propargylic arenes
	2.3 C–N bond formation in nitromethane
	2.4 Etherification reaction in nitromethane
	2.5 Oxidation of alcohols in nitromethane
	2.6 C–C and C–X (C-heteroatom) bond formation in nitromethane
	2.7 Synthesis of heterocycles
		2.7.1 Synthesis of O-heterocycles
		2.7.2 Synthesis of N-heterocycles
			2.7.2.1 Synthesis of substituted quinolines
			2.7.2.2 Synthesis of substituted isoquinolines
	2.8 Dual role of nitromethane
		2.8.1 Asymmetric allylic alkylation
		2.8.2 Synthesis of β-nitro-α-hydroxy esters
		2.8.3 Synthesis of bisarylmethanes and dithioacetals
		2.8.4 Asymmetric Michael addition reaction
		2.8.5 Coupling reaction
		2.8.6 Alkali-cyanide-free synthesis of α-iminonitriles
	2.9 Conclusions
	References
3. Tert-butyl hydroperoxide (TBHP)-mediated cross-coupling reactions
	3.1 Introduction
	3.2 Examples of TBHP in C–C and C–X (X = heteroatom) cross-coupling reactions
		3.2.1 TBHP- and Rose-Bengal-mediated C(sp3)–O cross-coupling of oxy-functionalized N-heterocycles
		3.2.2 C–S cross-coupling reaction of xanthene with sulfonyl hydrazides
		3.2.3 TBHP-mediated synthesis of 2,3-diaryl-1,4-diketones via oxidative coupling of benzyl ketones in aqueous medium
		3.2.4 TBHP-mediated C–O oxidative cross-coupling of phenols and 2-aminoacetophenones
		3.2.5 TBHP-mediated cross-coupling using aldehyde or alcohol with N-chloramine
		3.2.6 TBHP-mediated oxidative cross-dehydrogenative coupling of quinoxalin-2(1H)-ones with 4-hydroxycoumarins, 4-hydroxy-6-methyl-2-pyrone and 2-hydroxy-1, 4-naphthoquinone
		3.2.7 TBHP-mediated dehydrogenative cross-oxidative coupling between methylarenes and acetanilides
		3.2.8 TBAI/TBHP-mediated oxidative cross-coupling of ketones with phenols and carboxylic acids
		3.2.9 TBHP-mediated oxidative coupling of bisnucleophiles and isocyanides
		3.2.10 TBHP-promoted reaction between quinazoline-3-oxides and primary benzyl amines: C–N bond formation
		3.2.11 TBHP-mediated direct oxidative aryl–aryl cross-coupling in a regioselective manner
		3.2.12 TBHP-mediated oxidative cross-coupling between sp3 C–H and sp2 P–H centers
		3.2.13 TBHP-mediated synthesis of β-ketosulfones via oxidative cross-coupling of vinyl acetates with sulfonyl hydrazides
		3.2.14 TBHP-promoted oxidative C–N bond formation
		3.2.15 TBHP-promoted various important cross-coupling reactions
			3.2.15.1 Oxidative sp3 C–H bond functionalization
			3.2.15.2 Cross-coupling reaction of 4-hydroxydithiocoumarin
			3.2.15.3 Synthesis of 5-aminopyrazoles
			3.2.15.4 Synthesis of unsymmetrical bis-acyl ketals
			3.2.15.5 Synthesis of functionalized 2H-azirine
			3.2.15.6 TBHP mediated synthesis of highly functionalized isoquinolinones and quinolinones
	3.3 Conclusions
	References
4. Applications of Cyrene and ethyl lactate bio-based solvents for organic transformations
	4.1 Introduction
	4.2 Cyrene-mediated organic reactions
	4.3 Ethyl-lactate-mediated organic transformations
		4.3.1 Transamination
		4.3.2 Olefin metathesis
		4.3.3 Carbonyl group transformations
		4.3.4 Dehydration of sugars
		4.3.5 Heterocyclizations
		4.3.6 Multicomponent reactions
	4.4 Conclusions
	List of abbreviations
	References
5. Solid-phase platform: a nonconventional synthetic route for the current organic synthesis of diversified heterocyclic and carbocyclic framework
	5.1 Introduction
	5.2 Solid-phase synthesis (SPS)
		5.2.1 Advantages of SPS
		5.2.2 Limitations of SPS
		5.2.3 Definitions of some expressions associated with SPS
	5.3 Solid-phase platform
		5.3.1 Polymer-supported solid phase
		5.3.2 Clay and clay-supported reagents
		5.3.3 Silica gel as solid-state platform
		5.3.4 Alumina as solid-phase platform
			5.3.4.1 Activated neutral alumina (Al2O3)
			5.3.4.2 Activated alumina ball
			5.3.4.3 KF/alumina
	5.4 Construction of carbocyclic framework on solid support
		5.4.1 Diels–Alder reaction
			5.4.1.1 Synthesis of 3,4,5-trisubstituted cyclohexanones
		5.4.2 Electrocyclic reaction
			5.4.2.1 Synthesis of multiple core structure libraries
		5.4.3 Oligomerization reaction
	5.5 Formation of heterocyclic framework on solid phase
		5.5.1 Nitrogen-containing heterocycle
			5.5.1.1 Synthesis of hydroxyaziridines
			5.5.1.2 Synthesis of 2,4-pyrrolidinedionescombinatorial library
			5.5.1.3 Synthesis of 2,3-dihydro-4-pyridones derivatives
			5.5.1.4 Synthesis of structurally diverse pyrazolones
			5.5.1.5 Synthesis of 2-[[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]oxy]-1-phenylethanone
			5.5.1.6 Synthesis of 4,5-dihydro-1H-pyrazoles
			5.5.1.7 Synthesis of aromatic 1,2-diazines
			5.5.1.8 Synthesis of 4-amino-3,4-dihydro-2(1H)-quinolinones
			5.5.1.9 Synthesis of 2-aryl-1,2,3,4-tetrahydro-4-quinolones
			5.5.1.10 Synthesis of tetrahydroquinolines
			5.5.1.11 Electrophilic aromatic substitution
				5.5.1.11.1 Synthesis of 1,2,6-trisubstituted 1,2,3,4-tetrahydroisoquinoline
			5.5.1.12 Nucleophilic aromatic substitution
				5.5.1.12.1 Synthesis of 3,4-disubstituted-7-carbamoyl-1,2,3,4-tetrahydroquinoxalin-2-ones
			5.5.1.13 Synthesis of quinoxalines
			5.5.1.14 Synthesis of 2-substituted indole
			5.5.1.15 Synthesis of indole analogs
			5.5.1.16 Synthesis of trisubstituted indoles
			5.5.1.17 Synthesis of 1,2-disubstituted benzimidazoles
			5.5.1.18 Synthesis of 1H-indazoles
			5.5.1.19 Synthesis of spiroindoline
			5.5.1.20 Synthesis of five- and six-membered ring lactams
			5.5.1.21 Synthesis of cyclic ureas and thioureas
			5.5.1.22 Synthesis of xanthines
			5.5.1.23 Multicomponent reactions (MCRs)
				5.5.1.23.1 Features of multicomponent reactions
				5.5.1.23.2 Synthesis of quinoline derivatives
				5.5.1.23.3 Synthesis of 2-arylquinoline-4-carboxylic acid
				5.5.1.23.4 Synthesis of hydantoin 4-imides
				5.5.1.23.5 Synthesis of imidazo[1,2-a]-annulated pyridines, pyrazines and pyrimidines
				5.5.1.23.6 Synthesis of spiro[pyrrolo-4,10′-indeno[1,2-b]quinoline] and spiro[indololo-3,4′-indeno[1,2-b]pyridine]
		5.5.2 Oxygen-bearing heterocycle
			5.5.2.1 Synthesis of epoxide scaffolds
			5.5.2.2 Synthesis of substituted 3,4-dihydro-2H-pyrans
			5.5.2.3 Synthesis of 2-substituted benzofurans
			5.5.2.4 Radical reactions
				5.5.2.4.2 Synthesis of 3-substituted dihydrobenzofuran
				5.5.2.4.1 Synthesis of dihydrobenzofuran derivatives
			5.5.2.5 Synthesis of functionalized γ- and δ-lactones
			5.5.2.6 Synthesis of 2-amino-substituted isoflav-3-enes
			5.5.2.7 Synthesis of flavones
		5.5.3 Sulfur-containing heterocycles
			5.5.3.1 Synthesis of substituted thiophenes
		5.5.4 Solid-phase syntheses of miscellaneous heterocycle
			5.5.4.1 Synthesis of isoquinoline- and isoxazoline-containing heterocycles
			5.5.4.2 Synthesis of benzoxazoles
			5.5.4.3 Syntheses of cyclic peptides with endocyclic biaryl ether bonds
			5.5.4.4 Synthesis of isoxazolidines
			5.5.4.5 Synthesis of benzoxazinone
			5.5.4.6 Synthesis of peptidosulfonamides
			5.5.4.7 Synthesis of piperidino-thiomorpholine
			5.5.4.8 Synthesis of di[benzo(d)thiazol-3(2H)-yl]methane
			5.5.4.9 Synthesis of benzirnidazoles and 1,3-benzothiazole
			5.5.4.10 Synthesis of 2-aroylbenzo[b]furans, 1,3-thiazoles and 3-aryl-5,6-dihydroimidazo[2,1-b][1,3]thiazoles
	5.6 Conclusions
	References
6. Nonconventional solvents for the isolation of natural products
	6.1 Introduction
	6.2 Subcritical water
		6.2.1 Features of subcritical water
		6.2.2 Applications of subcritical water for the isolation of natural products as a green solvent
			6.2.2.1 Alkaloids
			6.2.2.2 Flavonoids
			6.2.2.3 Lignans
			6.2.2.4 Steroids
			6.2.2.5 Terpenoids
	6.3 Ionic liquid
		6.3.1 Features of ionic liquid
			6.3.1.1 Sugar containing ionic liquids
			6.3.1.2 Alkaloid containing ionic liquids
			6.3.1.3 Lipid-containing ionic liquids
		6.3.2 Applications of ionic liquid for the isolation of natural products as a green solvent
			6.3.2.1 Flavonoids
			6.3.2.2 Alkaloids
			6.3.2.3 Terpenoids
			6.3.2.4 Phenylpropanoids
			6.3.2.5 Quinones
			6.3.2.6 Fats
			6.3.2.7 Essential oils
			6.3.2.8 Carotenoids
			6.3.2.9 Saponins
			6.3.2.10 Vitamins
	6.4 Bio-based solvents
		6.4.1 Features of bio-based solvents
		6.4.2 Synthesis and applications of bio-based solvents
			6.4.2.1 Alcohols
			6.4.2.2 Esters
			6.4.2.3 Alkanes and aromatics
			6.4.2.4 Ethers
	6.5 Liquefied dimethyl ether
		6.5.1 Features of liquefied dimethyl ether
		6.5.2 Applications of liquefied dimethyl ether for the isolation of natural products as a green solvent
	6.6 Conclusions
	References
7. Role of nonconventional solvents in drug design
	7.1 Introduction
	7.2 Drug design
	7.3 The ionic liquids’ role in the pharmaceutical combination synthesis
		7.3.1 Ionic liquids as catalyst
		7.3.2 Ionic liquids as solvent, cosolvent and surfactant
		7.3.3 Ionic liquids in crystallization of drugs
		7.3.4 Ionic liquids in drug delivery
		7.3.5 Ionic liquids and biological activity
	7.4 Deep eutectic as catalyst and solvent in the organic reactions
	7.5 Conclusions
	References
8. Industrial applications of nonconventional solvents
	8.1 Introduction
	8.2 Polyethylene glycol (PEG)
	8.3 Glycerol
	8.4 Cyclopentylmethyl ether (CPME)
	8.5 2-Methyltetrahydrofuran (2-MeTHF)
	8.6 Ethyl lactate
	8.7 Conclusions
	References
9. Impact of nonconventional solvents on environment
	9.1 Introduction
		9.1.1 Volatility
		9.1.2 Chemical properties
		9.1.3 Flammability and explosiveness
	9.2 Solvent selection methods
	9.3 Methods to evaluate greenness of solvents
	9.4 Restorative actions to reduce hazards due to conventional solvents
		9.4.1 Water
		9.4.2 Supercritical fluids (SCFs)
		9.4.3 Bio-based solvent
		9.4.4 Surfactant-based solutions
		9.4.5 Deep eutectic solvent (DES)
		9.4.6 Ionic liquids (ILs)
		9.4.7 Magnetic ionic liquids (MILs)
		9.4.8 No solvent approach
	9.5 Conclusions
	Abbreviations
	References
Index