Table of Contents

Cover

Title Page

List of Contributors

Chapter 1: The Applications of Water as Reagents in Organic Synthesis

1.1 Introduction
1.2 Incorporation of Hydrogen Atom from the Water
1.3 Incorporation of Oxygen Atom from the Water
1.4 Incorporation of Hydroxyl Group from Water
1.5 Traceless Promotion of the Reactions by Water
1.6 Conclusions
References

Chapter 2: The Applications of Toluene and Xylenes

2.1 Application of Toluene and Xylenes as Reagents
2.2 Oxidation of Methyl Group into Common Functionalities
2.3 Application of Methyl Group as Acyl Building Block
2.4 Application as Alkyl Building Block
2.5 Application as Esters Building Block
2.6 Application as Alcohols Building Block
References

Chapter 3: The Applications of 1,4-Dioxane, THF, and Ethers as Versatile Building Blocks in Organic Synthesis

3.1 Introduction
3.2 Cleavage of C(sp³)−H of Ethers
3.3 Cleavage of C−O of Ethers
3.4 Cleavage of C−C Bonds of Ethers
3.5 Conclusion
References

Chapter 4: The Application of Dichloromethane and Chloroform as Reagents in Organic Synthesis

4.1 The Application of Dichloromethane and Chloroform as Reagents in Organic Synthesis
References

Chapter 5: The Applications of Acetone and Ethyl Acetate

5.1 Acetone
5.2 Ethyl Acetate
References

Chapter 6: N,N-Dimethylformamide and N,N-Dimethylacetamide as Carbon, Hydrogen, Nitrogen, and/or Oxygen Sources

6.1 Introduction
6.2 Amination
6.3 Amidation and Thioamidation
6.4 Amidination
6.5 Formylation and Related Domino Reactions
6.6 Carbonylation
6.7 Cyanation
6.8 Insertion Reactions
6.9 Miscellaneous Reactions
Acknowledgments
References

Chapter 7: The Applications of DMSO

7.1 A Brief Introduction of DMSO
7.2 Name Reactions
7.3 As Reaction Reagents
7.4 As Multifunctional Catalyst/Reagent in Self-Sorting Reaction System
7.5 Summary and Perspectives
Acknowledgments
References

Chapter 8: Acetonitrile as Reagents in Organic Synthesis: Reactions and Applications

8.1 Introduction
8.2 Transition-Metal-Catalyzed Cross-Coupling of Acetonitrile and Nitriles
8.3 Free-Radical-Initiated C−H Functionalization of Acetonitrile and Nitriles
8.4 Summary and Outlook
Acknowledgments
References

Chapter 9: The Applications of Nitromethane as Reagent and Solvent in Organic Synthesis

9.1 Introduction
9.2 Reactions with Aldehydes
9.3 Reactions with Imines
9.4 Reactions with Ketones
9.5 Michael Reaction
9.6 Other Reactions
References

Chapter 10: Alcohol as a Reagent in Homogeneous Catalysis

10.1 Introduction
10.2 Alcohol as O-nucleophile
10.3 Alcohol Oxidation or α-C−H Functionalization (Alcohol as C-nucleophile)
10.4 Alcohol as Electrophile
10.5 Conclusion
References

Chapter 11: Synchronous Application of Hydrocarbons as Solvents and Reagents in Transition-Metal Catalysis

11.1 Introduction
11.2 Aromatic Hydrocarbons
11.3 Aliphatic Hydrocarbons
11.4 Conclusions
Acknowledgments
References

Index

End User License Agreement

List of Illustrations

Chapter 1: The Applications of Water as Reagents in Organic Synthesis

Scheme 1.1 Enantioselective synthesis of (+)-sertraline and (+)-indatraline.
Scheme 1.2 Catalyst-free sulfonylation of activated alkenes in water.
Scheme 1.3 Silver(I)-catalyzed hydroazidation of ethynyl carbinols.
Scheme 1.4 Silver-catalyzed hydroazidation of alkynes and the application to access to 1,5-fused 1,2,3-triazoles.
Scheme 1.5 Formation of 2H-1,2,3-triazol-4-ols from α-azido esters.
Scheme 1.6 Triphenylphosphinecarboxamide: An effective reagent for the reduction of azides.
Scheme 1.7 Visible-light-induced hydrodifluoromethylation of alkenes.
Scheme 1.8 Two cascade reactions to synthesize substituted furocoumarins.
Scheme 1.9 Hydroxyphosphinylation reaction of 3-cyclopropylideneprop-2-en-1-ones.
Scheme 1.10 TfOH-catalyzed domino cycloisomerization/hydrolytic defluorination of 2,3-allenyl perfluoroalkyl ketones.
Scheme 1.11 Synthesis of benzyl derivatives via oxidation of stilbenes in an I₂–H₂O system.
Scheme 1.12 Copper-catalyzed oxidative cyclization of 1,5-enynes to access to 3-formyl-1-indenones.
Scheme 1.13 Rh(II)-catalyzed denitrogenative hydration reaction of N-sulfonyl-1,2,3-triazoles.
Scheme 1.14 The Wacker oxidation reaction for the synthesis of methyl ketones.
Scheme 1.15 Efficient and highly aldehyde selective Wacker oxidation.
Scheme 1.16 Pd(II)-catalyzed direct oxygenation of allylic C−H bond with H₂O.
Scheme 1.17 Anti-Markovnikov oxidation of β-alkyl styrenes with H₂O as the terminal oxidant.
Scheme 1.18 Synthesis of arylcarboxyamides from aryl diazonium salts and isocyanides.
Scheme 1.19 Synthesis of benzamides by a multicomponent reaction involving arynes, isocyanides, and H₂O.
Scheme 1.20 Pd(II)-catalyzed nitrile-directed C−H activation for the synthesis of fluorenones.
Scheme 1.21 Ruthenium-catalyzed cyclization of aromatic nitriles with alkenes.
Scheme 1.22 Synthesis of 3,3-disubstituted 2,3-dihydroazanaphthoquinones.
Scheme 1.23 Cu(II)-catalyzed monohydration of methylenemalononitriles.
Scheme 1.24 Enantioselective approach to polycyclic polyprenylated acylphloroglucinols via CAIMCP.
Scheme 1.25 Visible-light-initiated direct oxysulfonylation of alkenes.
Scheme 1.26 I₂/aqueous TBHP-catalyzed coupling of amides with methylarenes.
Scheme 1.27 Synthesis of monofluorinated arylhydrazones.
Scheme 1.28 Oxidation of aliphatic C−H bonds in amino-containing molecules.
Scheme 1.29 Cu(I)-catalyzed Aza-Diels–Alder/nucleophilic addition/ring-opening reaction.
Scheme 1.30 Cu/Fe-cocatalyzed Meyer–Schuster-like rearrangement of propargylic amines.
Scheme 1.31 [(NHC)Au^I]-catalyzed acid-free alkyne hydration.
Scheme 1.32 Regiospecific hydration of N-(diphenylphosphinoyl)propargyl amines.
Scheme 1.33 Pt(II)-catalyzed hydrative carbocyclizations of oxo-alkyne-nitrile functionalities.
Scheme 1.34 Ruthenium-catalyzed intramolecular carbocyclization of alkynes.
Scheme 1.35 Pd/Cu-catalyzed intermolecular cyclization of enediyne compounds and alkynes.
Scheme 1.36 Pd(II)-catalyzed bimolecular carbocyclizations of enediynes to 2,6-diacylnaphthalenes.
Scheme 1.37 Copper-catalyzed intramolecular oxidative 6-exo-trig cyclization of 1,6-enynes.
Scheme 1.38 Intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes leading to spiro[4,5]trienones.
Scheme 1.39 Nitrative cyclization of N-aryl imines with t-BuONO to 3-nitroindoles.
Scheme 1.40 Cascade nitration/cyclization of 1,7-enynes with t-BuONO and H₂O.
Scheme 1.41 Synthesis of disubstituted isoxazoles from homopropargylic alcohol.
Scheme 1.42 Nitrative spirocyclization mediated by TEMPO.
Scheme 1.43 Nitrative cyclization of 1-ethynyl-2-(vinyloxy)benzenes with t-BuONO.
Scheme 1.44 Metal-free [4+2] annulation of arylalkynes with tert-butyl nitrite.
Scheme 1.45 Palladium-catalyzed oxidative 6-exo-trig cyclization of 1,6-enynes.
Scheme 1.46 Tunable cascade reactions of alkynols with alkynes.
Scheme 1.47 Rh(II)-catalyzed three-component reactions leading to β-aryl isoserine derivatives.
Scheme 1.48 Highly α-selective hydrolysis of α,β-epoxyalcohols.
Scheme 1.49 Difluorohydroxylation of indoles using Selectfluor as a fluorinating reagent.
Scheme 1.50 Halohydroxylation reaction of allenes.
Scheme 1.51 Lewis-acid-catalyzed synthesis of (E)-α,β-unsaturated acids.
Scheme 1.52 Rh(II)-catalyzed tandem reactions for the syntheses of dihydroisobenzofurans and indanones.
Scheme 1.53 Gold(I)-catalyzed ring-expanding spiroannulation of cyclopropenones with enynes.
Scheme 1.54 Anti-Markovnikov hydration of alkenes via triple relay catalysis.
Scheme 1.55 Pd-catalyzed transformation of terminal alkenes into primary allylic alcohols.
Scheme 1.56 Synthesis of N-aryl β-amino alcohols from aziridines, arynes, and water.
Scheme 1.57 PhI(OCOCF₃)₂-mediated cyclization of o-(1-alkynyl)benzamides.
Scheme 1.58 Carbohydroxylation of styrenes with aryldiazonium salts.
Scheme 1.59 Palladium-catalyzed C(sp³)–H hydroxylation with H₂O as the oxygen source.
Scheme 1.61 Rh(III)-catalyzed [3+2]/[5+2] annulation of 4-aryl 1,2,3-triazoles with internal alkynes.
Scheme 1.60 Synthesis of functionalized 2-hydroxyflavanone derivatives.
Scheme 1.62 Copper-catalyzed arylation/C−C bond activation to access to α-aryl ketones.
Scheme 1.63 Cu-catalyzed oxidative amidation–diketonization of terminal alkynes.
Scheme 1.64 I₂/TBHP-mediated synthesis of sulfonamides and β-arylsulfonyl enamines.
Scheme 1.65 Synthesis of substituted imidazopyridines and thiazoles from styrenes in water.
Scheme 1.66 Asymmetric hetero-Diels–Alder reaction of diazenes catalyzed by chiral silver phosphate.
Scheme 1.67 Rh (III)-catalyzed [3+2] annulation of 5-aryl-2,3-dihydro-1H-pyrroles with internal alkynes.
Scheme 1.68 Pd(II)-catalyzed ortho-trifluoromethylation of benzylamines.
Scheme 1.69 Base-promoted formal arylation of benzo[d]oxazoles with acyl chloride.
Scheme 1.70 Cu(II)-catalyzed CDC reaction between allylic C−H bonds and α-C−H bonds of ketones or aldehydes.

Chapter 2: The Applications of Toluene and Xylenes

Figure 2.1 Structure of Toluene and Xylene Isomers.
Figure 2.2 Conversion of Toluene Derivatives to Different Products.
Scheme 2.1
Scheme 2.2
Scheme 2.3
Scheme 2.4
Scheme 2.5
Scheme 2.6
Scheme 2.7
Scheme 2.8
Scheme 2.9
Scheme 2.10
Scheme 2.11
Scheme 2.12
Scheme 2.13
Scheme 2.14
Scheme 2.15
Scheme 2.16
Scheme 2.17
Scheme 2.18
Scheme 2.19
Scheme 2.20
Scheme 2.21
Scheme 2.22
Scheme 2.23
Scheme 2.24
Scheme 2.25
Scheme 2.26
Scheme 2.27
Scheme 2.28
Scheme 2.29
Scheme 2.30
Scheme 2.31
Scheme 2.32
Scheme 2.33
Scheme 2.34
Scheme 2.35
Scheme 2.36
Scheme 2.37
Scheme 2.38
Scheme 2.39
Scheme 2.40
Scheme 2.41
Scheme 2.42
Scheme 2.43
Scheme 2.44
Scheme 2.45
Scheme 2.46
Scheme 2.47
Scheme 2.48

Chapter 3: The Applications of 1,4-Dioxane, THF, and Ethers as Versatile Building Blocks in Organic Synthesis

Scheme 3.1 Autoxidation of diethyl ether at room temperature.
Scheme 3.2 Cross-dehydrogenative coupling reactions of ethers to form C−C, C−N, and C−O bonds.
Scheme 3.3 CDC reaction of ethers with 1, 3-dicarbonyl compounds to form C−C bonds.
Scheme 3.4 CDC reaction of ethers with ketones to form C−C bonds.
Scheme 3.5 CDC reaction of ethers with α-amino carbonyl compounds to form C−C bonds.
Scheme 3.6 CDC reaction of ethers with N, N-dialkylanilines to form tricyclic compounds.
Scheme 3.7 CDC reaction of ethers with olefins to construct allylic ethers.
Scheme 3.8 CDC reaction of ethers with benzene derivatives.
Scheme 3.9 CDC reaction of ethers with benzothiazole, benzoxazole or benzimidazole.
Scheme 3.10 More CDC reactions of ethers with azoles.
Scheme 3.11 Regioselective CDC reaction of ethers with indoles.
Scheme 3.12 Regioselective CDC reactions of ethers with coumarins and flavones.
Scheme 3.13 Regioselective CDC reaction of ethers with quinoline N-oxides.
Scheme 3.14 Tandem reaction of 2-alkynylbenzaldoximes with cyclic ethers.
Scheme 3.15 Tandem reaction of 2-alkynylbenzaldoximes with cyclic ethers.
Scheme 3.16 α-C−H amination of ethers with imidazole, 1H-pyrazole, 1H-1,2,4-triazole, and benzimidazole.
Scheme 3.17 Other azoles used in α-C−H amination of ethers.
Scheme 3.18 α-C−H amination of ethers with N-alkoxyamides.
Scheme 3.19 Two different methods to form THP ether and THF ether.
Scheme 3.20 CrCl₂-mediated C−O bond formation of ether with alcohol.
Scheme 3.21 The CDC reaction of ethers with phenol derivatives or β-ketoesters.
Scheme 3.22 The CDC reaction of ethers with oximes.
Scheme 3.23 The CDC reaction of ethers with carboxylic acids to form C−O bonds.
Scheme 3.24 α-Acyloxylation reaction of ethers with diverse substrates.
Scheme 3.25 C−S bond formation of ethers with various S sources.
Scheme 3.26 Early examples of the addition of ethers to CC bonds.
Scheme 3.27 Recent examples of the addition of ethers to CC bonds with transition metal catalysts.
Scheme 3.28 More examples of the addition of ethers to CC bonds with transition metal catalysts.
Scheme 3.29 Addition of ethereal radical to CC bonds followed by insertion to CC bonds.
Scheme 3.30 The addition of ethers to CC bonds with transition metal catalysts.
Scheme 3.31 Proposed mechanism involving ethereal C−H oxidation addition on Rh(I).
Scheme 3.32 Decarboxylative alkenylation and alkylation reactions with ethers.
Scheme 3.33 Tunable decarboxylative alkylation reactions of cinnamic acids with ethers.
Scheme 3.34 Plausible mechanisms for radical alkenylation and alkynylation of ethers.
Scheme 3.35 Representative examples of radical alkenylation and alkynylation of ethers.
Scheme 3.36 Et₃B-promoted α-C−H hydroxyalkylation of ethers under air.
Scheme 3.37 Lewis acids-/air-mediated α-C−H hydroxyalkylation or aminoalkylation of ethers.
Scheme 3.38 A plausible mechanism for the metal-catalyzed intermolecular carbenoid insertion with alkanes or α-C−H bond of ethers.
Scheme 3.39 Rh-catalyzed asymmetric C−H insertion into THF.
Scheme 3.40 C(sp³)−H arylation of THF with arylmagnesium bromide.
Scheme 3.41 Oxidative C(sp³)−H arylation of ethers with arylboronic acids.
Scheme 3.42 C−O cleavage under acidic conditions.
Scheme 3.43 C−O cleavage under Lewis acidic conditions.
Scheme 3.44 C−O cleavage under organometallic reagents.
Scheme 3.45 C−O cleavage involving peroxides.
Scheme 3.46 C−O cleavage involving ZnMe₂ and O₂.
Scheme 3.47 Synthesis of heterocycles involving C−O cleavage.
Scheme 3.48 Direct aryl hydroxylation using 1,4-dioxane as the source of the hydroxyl group.
Scheme 3.49 C−C cleavage of ethers.

Chapter 4: The Application of Dichloromethane and Chloroform as Reagents in Organic Synthesis

Scheme 4.1
Scheme 4.2
Scheme 4.3
Scheme 4.4
Scheme 4.5
Scheme 4.6
Scheme 4.7
Scheme 4.8
Scheme 4.9
Scheme 4.10
Scheme 4.11
Scheme 4.12
Scheme 4.13
Scheme 4.14
Scheme 4.15
Scheme 4.16
Scheme 4.17
Scheme 4.18
Scheme 4.19
Scheme 4.20
Scheme 4.21
Scheme 4.22
Scheme 4.23
Scheme 4.24
Scheme 4.25
Scheme 4.26
Scheme 4.27
Scheme 4.28
Scheme 4.29
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Scheme 4.31
Scheme 4.32
Scheme 4.33
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Scheme 4.35
Scheme 4.36
Scheme 4.37
Scheme 4.38
Scheme 4.39
Scheme 4.40
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Scheme 4.42
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Scheme 4.48
Scheme 4.49
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Scheme 4.55
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Scheme 4.57
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Scheme 4.59
Scheme 4.60
Scheme 4.61
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Scheme 4.64
Scheme 4.65
Scheme 4.66
Scheme 4.67
Scheme 4.68
Scheme 4.69
Scheme 4.70
Scheme 4.71
Scheme 4.72
Scheme 4.73
Scheme 4.74
Scheme 4.75
Scheme 4.76
Scheme 4.77
Scheme 4.78
Scheme 4.79
Scheme 4.80
Scheme 4.81

Chapter 5: The Applications of Acetone and Ethyl Acetate

Scheme 5.1 General form of aldol reaction involving ketone as nucleophile.
Scheme 5.2 Proline-catalyzed asymmetric aldol reaction of acetone and aldehydes.
Scheme 5.3 Enamine-activation-based mechanism of the proline-catalyzed aldol reaction.
Scheme 5.4 DMTC-catalyzed asymmetric aldol reaction of acetone and aldehydes.
Figure 5.1 Some chiral amines used in asymmetrical aldol reaction.
Scheme 5.5 Asymmetrical aldol reactions of isatins and acetone.
Scheme 5.6 Benzyl-alcohol-based Claisen–Schmidt reaction.
Scheme 5.7 l-proline-catalyzed synthesis of enones and cyclohexanones.
Scheme 5.8 l-Proline-catalyzed asymmetric Mannich reaction.
Scheme 5.9 Three-component Mannich reaction catalyzed by chiral sulfoxide.
Scheme 5.10 Asymmetric Mannich reactions of trifluoromethyl ketimines and acetone.
Scheme 5.11 Asymmetrical Mannich reactions of 3-substituted-2H-1,4-benzoxazines and acetone.
Scheme 5.12 Asymmetrical Mannich reactions of benzo[e][1,2,3]oxathiazine 2,2-dioxides and acetone.
Scheme 5.13 Enantioselective synthesis of β-amino ketones of five-membered structure.
Scheme 5.14 Asymmetric Mannich reaction of seven-membered ketimines.
Scheme 5.15 Asymmetric Mannich reactions of different cyclic ketimines and acetone.
Scheme 5.16 The synthesis of alcohols and substituted malonitrile using acetone.
Scheme 5.17 Different synthesis of benzodiazepines.
Scheme 5.18 Multicomponent synthesis of benzodiazepinyl phosphonates.
Scheme 5.19 Acetone-based multicomponent synthesis of azine heterocyles.
Scheme 5.20 Acetone-based multicomponent synthesis of pyridin-2(1H)-one.
Scheme 5.21 Divergent syntheses involving the single nucleophilic addition of the methyl of acetone.
Scheme 5.22 Reactions involving the transformation of both methyl groups in acetone.
Scheme 5.23 Acetone-based three-component reactions for the synthesis of anilines.
Scheme 5.24 Acetone-participated multicomponent reactions for pyridine synthesis.
Scheme 5.25 Acetone-based three-component synthesis of quinolines.
Scheme 5.26 Cross-coupling reactions of acetone with aryl halides/tosylates.
Scheme 5.27 Carbonylative coupling reaction of aryl iodide, CO, and acetone.
Scheme 5.28 Selective acetylation of primary alcohols with ethyl acetate.
Scheme 5.29 Selective acetylation of the primary alcohols in carbohydrates.
Scheme 5.30 Selective acetylation of thioglycosides.
Scheme 5.31 NHC-catalyzed acetylation of secondary alcohols.
Scheme 5.32 Lanthanum(III) -catalyzed acetylation of secondary/tertiary alcohols.
Scheme 5.33 Enzyme-catalyzed acetylation of bile acids.
Scheme 5.34 Asymmetric synthesis of acetates via ketone-based acetylation.
Scheme 5.35 Transesterification between ethers and ethyl acetate.
Scheme 5.36 MWI-assisted amidation of ethyl acetate.
Scheme 5.37 Enzymatic resolution of primary amines via ethyl-acetate-based acetylation.
Scheme 5.38 Acetylation of sulfonamides.
Scheme 5.39 Synthesis of tertiary alcohols using C-nucleophiles and ethyl acetate.
Scheme 5.40 n-BuLi-promoted α-acetylation of phosphine oxide.
Scheme 5.41 Nucleophilic addition of the α-carbon in ethyl acetate to acrolein.
Scheme 5.42 Ethyl-acetate-participated synthesis of pyridin-2-ones.

Chapter 6: N,N-Dimethylformamide and N,N-Dimethylacetamide as Carbon, Hydrogen, Nitrogen, and/or Oxygen Sources

Scheme 6.1
Scheme 6.2
Scheme 6.3
Scheme 6.4
Scheme 6.5
Scheme 6.6
Scheme 6.7
Scheme 6.8
Scheme 6.9
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Scheme 6.22
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Figure 6.43
Scheme 6.44
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Scheme 6.75
Scheme 6.76
Scheme 6.77
Scheme 6.78
Scheme 6.79
Scheme 6.80
Scheme 6.81
Scheme 6.82
Scheme 6.83

Chapter 7: The Applications of DMSO

Scheme 7.1
Scheme 7.2
Scheme 7.3
Scheme 7.4
Scheme 7.5
Scheme 7.6
Scheme 7.7
Scheme 7.8
Scheme 7.9
Scheme 7.10
Scheme 7.11
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Scheme 7.21
Scheme 7.22
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Scheme 7.55
Scheme 7.56
Scheme 7.57
Scheme 7.58
Scheme 7.59
Scheme 7.60
Scheme 7.61
Scheme 7.62

Chapter 8: Acetonitrile as Reagents in Organic Synthesis: Reactions and Applications

Scheme 8.1 S_NAr of aryl fluorides with secondary nitriles and KHMDS.
Scheme 8.2 Proposed mechanism for the addition of secondary nitriles to fluoroarenes.
Scheme 8.3 Ruthenium complex-catalyzed direct addition of acetonitrile to aldehydes.
Scheme 8.4 Ruthenium complex-catalyzed direct addition of acetonitrile to imines.
Scheme 8.5 Palladium-catalyzed decarboxylative coupling of cyanoacetate salts with aryl halides and triflates for the synthesis of a-aryl nitriles.
Scheme 8.6 Synthesis of anastrozole.
Scheme 8.7 Palladium-catalyzed R-arylation of nitriles.
Scheme 8.8 Catalytic α-arylation of nitriles with aryl bromides by Pd(OAc)₂/16.
Scheme 8.9 Catalytic α-arylation of nitriles with chlorobenzene by Pd(OAc)₂/16.
Scheme 8.10 Palladium-catalyzed coupling of α-trimethylsilylpropionitrile.
Scheme 8.11 Palladium-catalyzed coupling of α-trimethylsilylcyclohexanecarbonitrile.
Scheme 8.12 Palladium-catalyzed coupling of zinc cyanoalkyl reagents of secondary nitriles.
Scheme 8.13 Synthetic application for the preparation of verapamil.
Scheme 8.14 Palladium-catalyzed carbonylation of aryl iodides and trimethylsilylacetonitrile.
Scheme 8.15 Palladium-catalyzed carbonylative α-arylation to β-ketonitriles.
Scheme 8.16 Palladium-catalyzed site-selective cyanomethylation of unactivated C(sp³)−H bonds.
Scheme 8.17 Catalyst-contorlled α-monoallylation of aryl acetonitriles.
Scheme 8.18 Palladium-catalyzed allylation of nitriles with allyl alcohol activated by CO₂.
Scheme 8.19 Proposed CO₂-catalyzed C−O bond activation.
Scheme 8.20 Ni-catalyzed synthesis of α-arylnitriles.
Scheme 8.21 Copper-catalyzed aerobic oxidative coupling of aromatic alcohols and acetonitrile to β-ketonitriles.
Scheme 8.22 Probable reaction mechanism.
Scheme 8.23 Rh-catalyzed preparation of reduced Knoevenagel adducts with CO as a deoxygenative agent.
Scheme 8.24 Bond dissociation energy of the C−H bond.
Scheme 8.25 1,2-Ayl migration reaction of unactivated alkenes with acetonitrile under metal-free conditions.
Scheme 8.26 Activated nitriles with 1,2-diaryl allylic alcohols.
Scheme 8.27 A possible mechanism of nitriles with 1,2-diaryl allylic alcohols.
Scheme 8.28 Copper Copper-catalyzed 1,2-aryl migration reaction of unactivated alkenes with acetonitriles.
Scheme 8.29 Metal Metal-promoted 1,2-alkylarylation of activated alkenes with acetonitriles.
Scheme 8.30 Nitro Nitro-substituted oxindoles obtained via radical cascade reaction.
Scheme 8.31 Visible-light-promoted 1,2-alkylarylation of activated alkenes with acetonitriles.
Scheme 8.32 Copper-promoted 1,2-alkylarylation of unactivated alkenes with acetonitriles.
Scheme 8.33 Copper Copper-promoted 1,2-oxylalkylation of unactivated alkenes with acetonitrile.
Scheme 8.34 1,2-oyalkylation of activated alkenes with acetonitrile.
Scheme 8.35 Copper-catalyzed 1,2-oyalkylation of unactivated alkenes with acetonitrile.
Scheme 8.36 Copper-catalyzed 1,2-oxylalkylation of olefinic amides with acetonitrile.
Scheme 8.37 Three-component carboetherification of unactivated alkenes with acetonitrile and alcohols.
Scheme 8.38 Three-component reactions of alkenes with alkylnitriles and water.
Scheme 8.39 1,2-Hydroalkylation of unactivated alkenes with acetonitrile.
Scheme 8.40 Radical CDC reaction of 1,3-dicarbonyl compounds with acetonitrile.

Chapter 9: The Applications of Nitromethane as Reagent and Solvent in Organic Synthesis

Scheme 9.1 Two-step continuous-flow transformations for the synthesis of nitro-containing compounds.
Scheme 9.2 Three-step continuous-flow transformations.

Chapter 10: Alcohol as a Reagent in Homogeneous Catalysis

Scheme 10.1
Scheme 10.2
Scheme 10.3
Scheme 10.4
Scheme 10.5
Scheme 10.6
Scheme 10.7
Scheme 10.8
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Scheme 10.69
Scheme 10.70
Scheme 10.71
Scheme 10.72
Scheme 10.73
Scheme 10.74

Chapter 11: Synchronous Application of Hydrocarbons as Solvents and Reagents in Transition-Metal Catalysis

Scheme 11.1
Scheme 11.2
Scheme 11.3
Scheme 11.4
Scheme 11.5
Scheme 11.6
Scheme 11.7
Scheme 11.8
Scheme 11.9
Scheme 11.10
Scheme 11.11
Scheme 11.12
Scheme 11.13
Scheme 11.14
Scheme 11.15
Scheme 11.16
Scheme 11.17
Scheme 11.18
Scheme 11.19
Scheme 11.20
Scheme 11.21
Scheme 11.22
Scheme 11.23
Scheme 11.24
Scheme 11.25
Scheme 11.26
Scheme 11.27
Scheme 11.28
Scheme 11.29
Scheme 11.30
Scheme 11.31
Scheme 11.32
Scheme 11.33
Scheme 11.34
Scheme 11.35
Scheme 11.36
Scheme 11.37
Scheme 11.38
Scheme 11.39
Scheme 11.40
Scheme 11.41
Scheme 11.42
Scheme 11.43
Scheme 11.44
Scheme 11.45
Scheme 11.46
Scheme 11.47
Scheme 11.48
Scheme 11.49
Scheme 11.50
Scheme 11.51
Scheme 11.52
Scheme 11.53
Scheme 11.54
Scheme 11.55
Scheme 11.56
Scheme 11.57
Scheme 11.58
Scheme 11.59
Scheme 11.60
Scheme 11.61
Scheme 11.62
Scheme 11.63
Scheme 11.64
Scheme 11.65
Scheme 11.66
Scheme 11.67
Scheme 11.68
Scheme 11.69
Scheme 11.70
Scheme 11.71
Scheme 11.72
Scheme 11.73
Scheme 11.74
Scheme 11.75
Scheme 11.76
Scheme 11.77
Scheme 11.78
Scheme 11.79
Scheme 11.80
Scheme 11.81
Scheme 11.82
Scheme 11.83
Scheme 11.84
Scheme 11.85
Scheme 11.86
Scheme 11.87
Scheme 11.88
Scheme 11.89
Scheme 11.90
Scheme 11.91
Scheme 11.92
Scheme 11.93
Scheme 11.94
Scheme 11.95
Scheme 11.96
Scheme 11.97
Scheme 11.98
Scheme 11.99
Scheme 11.100
Scheme 11.101
Scheme 11.102
Scheme 11.103
Scheme 11.104
Scheme 11.105
Scheme 11.106
Scheme 11.107
Scheme 11.108
Scheme 11.109
Scheme 11.110
Scheme 11.111
Scheme 11.112
Scheme 11.113
Scheme 11.114
Scheme 11.115
Scheme 11.116
Scheme 11.117
Scheme 11.118
Scheme 11.119
Scheme 11.120
Scheme 11.121
Scheme 11.122

List of Tables

Chapter 2: The Applications of Toluene and Xylenes

Table 2.1 Physical properties

Chapter 3: The Applications of 1,4-Dioxane, THF, and Ethers as Versatile Building Blocks in Organic Synthesis

Table 3.1 Physical properties and C−H BDEs of some representative ethers and alkanes with comparable molecular weight

Chapter 4: The Application of Dichloromethane and Chloroform as Reagents in Organic Synthesis

Table 4.1 Examples for dichlorocarbene addition to alkene halides
Table 4.2 Examples for dichlorocarbene addition to alkenes bearing various functional groups

Chapter 5: The Applications of Acetone and Ethyl Acetate

Table 5.1 Asymmetric aldol reactions of acetone and aldehydes catalyzed by different chiral amines (selected examples)
Table 5.2 Selected examples of acetone-based E-selective Claisen–Schmidt reaction
Table 5.3 Selected examples of acetylation reactions employing ethyl acetate as acetylating reagent
Table 5.4 Selected examples of catalytic amidation of ethyl acetate
Table 5.5 Selected examples of the catalytic hydrogenation of ethyl acetate

Chapter 7: The Applications of DMSO

Table 7.1 DMSO properties
Table 7.2 Heterocyclic Molecules Prepared Through Self-Sorting Reactions.

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List of Contributors

Jian Cao

Hangzhou Normal University

Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education

Science Park of HZNU Hangzhou 311121

PR China

Narendra R. Chaubey

Banaras Hindu University

Department of Chemistry (Centre of Advanced Study) Institute of Science

Varanasi 221005

India

Zhengkai Chen

Zhejiang Sci-Tech University

Department of Chemistry

Hangzhou 310018

PR China

Xue-Qiang Chu

Soochow University

Key Laboratory of Organic Synthesis of Jiangsu Province

College of Chemistry, Chemical Engineering and Materials Science & Collaborative Innovation Center of Suzhou Nano Science and Technology

Suzhou 215123

PR China

Yi Fang

Soochow University

Key Laboratory of Organic Synthesis of Jiangsu Province

College of Chemistry, Chemical Engineering and Materials Science & Collaborative Innovation Center of Suzhou Nano Science and Technology

Suzhou 215123

PR China

Qing-He Gao

Xinxiang Medical University

School of Pharmacy

District of Hongqi

Henan Xinxiang 453003

PR China

Feng Han

State Key Laboratory for Oxo Synthesis and Selective Oxidation

Suzhou Research Institute of LICP

Lanzhou Institute of Chemical Physics (LICP)

Chinese Academy of Sciences

Lanzhou 730000

PR China

Shun-Jun Ji

Soochow University

Key Laboratory of Organic Synthesis of Jiangsu Province

College of Chemistry, Chemical Engineering and Materials Science & Collaborative Innovation Center of Suzhou Nano Science and Technology

Suzhou 215123

PR China

Jean Le Bras

CNRS – Université de Reims Champagne-Ardenne

Institut de Chimie Moléculaire de Reims

UMR 7312, B.P. 1039

51687 Reims Cedex 2

France

Ping Liu

Nanjing Normal University

College of Chemistry and Materials Science

Jiangsu Provincial Key Laboratory of Material Cycle Processes and Pollution Control

Jiangsu Collaborative Innovation Center of Biomedical Functional Materials

Nanjing 210023

PR China

Chao Liu

State Key Laboratory for Oxo Synthesis and Selective Oxidation

Suzhou Research Institute of LICP

Lanzhou Institute of Chemical Physics (LICP)

Chinese Academy of Sciences

Lanzhou 730000

PR China

Jacques Muzart

CNRS – Université de Reims Champagne-Ardenne

Institut de Chimie Moléculaire de Reims

UMR 7312, B.P. 1039

51687 Reims Cedex 2

France

Krishna Nand Singh

Banaras Hindu University

Department of Chemistry (Centre of Advanced Study) Institute of Science

Varanasi 221005

India

Jin-Bao Peng

Zhejiang Sci-Tech University

Department of Chemistry

Hangzhou 310018

PR China

Xinxin Qi

Zhejiang Sci-Tech University

Department of Chemistry

Xiasha Campus

Hangzhou 310018

PR China

Hongjun Ren

Zhejiang Sci-Tech University

Department of Chemistry

Hangzhou 310018

PR China

Johannes Schranck

Solvias AG

Römerpark 2

4303 Kaiseraugst

Switzerland

Neetu Singh

Banaras Hindu University

Department of Chemistry Centre of Advanced Study Institute of Science

Varanasi 221005

India

Peipei Sun

Nanjing Normal University

College of Chemistry and Materials Science

Jiangsu Provincial Key Laboratory of Material Cycle Processes and Pollution Control

Jiangsu Collaborative Innovation Center of Biomedical Functional Materials

Nanjing 210023

PR China

Wei Sun

State Key Laboratory for Oxo Synthesis and Selective Oxidation

Suzhou Research Institute of LICP

Lanzhou Institute of Chemical Physics (LICP)

Chinese Academy of Sciences

Lanzhou 730000

PR China

Anis Tlili

Université Lyon 1

Institute of Chemistry and Biochemistry (ICBMS-UMR CNRS 5246), CNRS

Villeurbanne France

Jie-Ping Wan

Jiangxi Normal University

College of Chemistry and Chemical Engineering

Nanchang 330022

PR China

Shun-Yi Wang

Soochow University

Key Laboratory of Organic Synthesis of Jiangsu Province College of Chemistry, Chemical Engineering and Materials Science & Collaborative Innovation Center of Suzhou Nano Science and Technology

Suzhou 215123

PR China

An-Xin Wu

Key Laboratory of Pesticide & Chemical Biology Ministry of Education College of Chemistry

Central China Normal University

Hubei Wuhan 430079

PR China

Xiao-Feng Wu

Zhejiang Sci-Tech University

Department of Chemistry Xiasha Campus

Hangzhou 310018

PR China

and

Universität Rostock

Leibniz-Institut für Katalyse e.V. an der

Albert-Einstein-Straße 29a

18059 Rostock

Germany

Chungu Xia

State Key Laboratory for Oxo Synthesis and Selective Oxidation

Suzhou Research Institute of LICP

Lanzhou Institute of Chemical Physics (LICP)

Chinese Academy of Sciences

Lanzhou 730000

PR China

Jia-Chen Xiang

Key Laboratory of Pesticide & Chemical Biology Ministry of Education College of Chemistry

Central China Normal University

Hubei Wuhan 430079

PR China

Li-Wen Xu

Hangzhou Normal University

Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education

Science Park of HZNU Hangzhou 311121

PR China

Guanghui Zhang

Purdue University

School of Chemical Engineering

West Lafayette IN 47907

USA