Green, sustainable chemistry involves the designing of chemical processes with a view to reducing or even eliminating the use and production of hazardous materials. Recent endeavors have focused on limiting the use of organic solvents and replacing them with new, environmentally benign media. The chemical industry is interested in these cost-effective, alternative solvents and processes. This book provides a broad overview of the three most commonly used green reaction media. Directed at synthetic organic chemists working in academic and industrial laboratories, it will also serve as a textbook for graduate courses on green chemistry. Successful green reactions are considered, and experimental sections at the ends of the chapters provide important practical details, with illustrations of potential applications. Sufficient information is included to allow selection of the most appropriate medium. Extensively referenced, the volume offers a point of entry into the detailed literature.

Professor Koichi Mikami is at the Department of Applied Chemistry, Tokyo Institute of Technology, Japan

Contributors

ix

Preface

xi

Introduction

1

(8)

Koichi Mikami

Green reaction media

1

(1)

Ionic liquids

2

(1)

Fluorous media

3

(2)

Supercritical carbon dioxide

5

(4)

References

7

(2)

Ionic liquids

9

(50)

Jonathan J. Jodry

Koichi Mikami

Historical background and synthesis

9

(7)

Historical background

9

(1)

Synthesis

10

(1)

Preparation of imidazolium halides

10

(2)

Anion metathesis

12

(1)

Functionalized imidazolium ionic liquids

13

(1)

Other types of ionic liquid

13

(2)

Purification

15

(1)

Physical properties

16

(13)

Melting point

16

(5)

Thermal stability

21

(1)

Polarity

21

(2)

Solubility

23

(2)

Viscosity

25

(1)

Acidity

26

(1)

Chirality

27

(1)

Toxicity and environmental issues

28

(1)

Applications as reaction media

29

(21)

Hydroformylation

30

(2)

Hydrogenation

32

(3)

The Friedel-Crafts reaction

35

(2)

Epoxidation

37

(2)

Palladium-catalyzed C-C bond formation

39

(1)

The Mizoroki-Heck reaction

39

(4)

The Suzuki-Miyaura cross-coupling reaction

43

(1)

Other palladium-catalyzed cross-coupling reactions

44

(1)

The Diels-Alder reaction

45

(3)

Biocatalysis in ionic liquids

48

(2)

The future of ionic liquids

50

(1)

Experimental part

51

(8)

Preparation of [bmim][Cl]

51

(1)

Preparation of [bmim][PF6]

52

(1)

Preparation of a chiral imidazolium ionic liquid

52

(1)

Enantioselective hydrogenation of methyl acetoacetate

52

(1)

Epoxidation of 2,2-dimethylchromene

53

(1)

Mizoroki-Heck reaction between butyl acrylate and iodobenzene under microwave irradiation

53

(1)

Diphenylacetylene by the Sonogashira coupling reaction

53

(1)

References

54

(5)

Fluorous solvents

59

(66)

Ilhyong Ryu

Hiroshi Matsubara

Charlotte Emnet

John A. Gladysz

Seiji Takeuchi

Yutaka Nakamura

Dennis P. Curran

Historical background

59

(3)

Physical properties

62

(18)

Key design elements in fluorous/organic liquid biphasic reactions

62

(1)

Commercial availability

63

(3)

Polarity

66

(1)

Solute solubilities

66

(3)

Fluorous solvent miscibilities

69

(1)

Partition coefficients and fluorophilicities

70

(9)

Toxicity and environmental issues

79

(1)

Applications as reaction media

80

(24)

Fluorous catalysts for fluorous biphasic systems

80

(1)

Hydroformylation

80

(1)

Hydrogenation

81

(1)

Catalytic hydroboration and hydrosilylation

81

(1)

Catalytic oxidation reactions

82

(3)

Coupling reactions

85

(3)

Fluorous acid and base catalysts

88

(4)

Enantioselective catalysts for fluorous biphasic systems

92

(1)

Reduction

92

(1)

Epoxidation

92

(2)

Protonation

94

(1)

Et2Zn or Et3Al addition to aldehydes

94

(2)

Heavy fluorous reagents

96

(1)

Fluorous tin hydrides

96

(1)

The Stille coupling reaction

96

(2)

Radical carbonylation reaction

98

(1)

Fluorous tin azide

99

(1)

Fluorous sulfide and sulfoxide

99

(1)

Other fluorous reagents

100

(1)

Heavy fluorous protecting groups

101

(1)

Trifluoroalkylsilyl protecting group

101

(1)

Fluorous alcohol protective group

102

(1)

Fluorous carboxylic acid protecting group

103

(1)

Light fluorous compounds and fluorous silica gel

104

(7)

Heavy and light fluorous molecules and separation strategy

104

(1)

Solid-phase extractions with fluorous silica gel

105

(1)

Light fluorous reagents

106

(1)

Light fluorous catalysts

107

(1)

Light fluorous scavengers

108

(1)

Light fluorous protecting groups

109

(2)

Fluorous reactions in supercritical carbon dioxide (scCO2) and fluorous triphasic reactions

111

(4)

Fluorous reactions in scCO2

111

(2)

Fluorous triphasic reactions

113

(2)

Experimental part

115

(10)

Asymmetric epoxidation of alkenes under fluorous biphasic conditions

115

(1)

Asymmetric addition of Et2Zn to benzaldehyde catalyzed by F13BINOL-Ti in an FC-72/organic biphasic system

115

(1)

Ugi four-components condensation

116

(1)

Synthesis of a tetrasaccharide using a fluorous protective group

116

(1)

Large-scale preparation of tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)tin hydride

117

(1)

The Stille coupling reaction with fluorous tin reactant under microwave irradiation

117

(1)

Fluorous Swern oxidation

118

(1)

Preparation of 4-methylacetophenone in the presence of a fluorous acetylacetonate palladium complex

118

(1)

The Mizoroki-Heck reaction using a fluorous palladacycle catalyst

118

(1)

Direct amide condensation using a fluorous phenylboronic acid

119

(1)

Esterification of alcohol with acetic anhydride using a fluorous scandium catalyst

119

(1)

References

119

(6)

Supercritical carbon dioxide

125

(58)

Christopher M. Rayner

R. Scott Oakes

Toshiyasu Sakakura

Hiroyuki Yasuda

Historical background

125

(1)

Physical properties

126

(5)

Fundamentals of supercritical fluids

126

(4)

Enhancement of solubilities in scCO2

130

(1)

Applications as reaction media

131

(30)

Background

131

(1)

Hydroformylation

132

(2)

Hydrogenation

134

(4)

Oxidation

138

(4)

Complex-catalyzed carbon-carbon bond formation

142

(3)

Diels-Alder reactions

145

(2)

Acid catalysis

147

(2)

Polymer synthesis

149

(3)

Biocatalysis

152

(2)

Utilization as a carbon resource

154

(4)

Miscellaneous reactions

158

(3)

Synthesis and separation

161

(9)

CO2/water two-phase system

161

(2)

CO2/ionic liquid two-phase system

163

(2)

Recoverable catalysts

165

(2)

Other separation processes

167

(2)

New CO2-philes

169

(1)

Experimental methods

170

(13)

Hydroformylation in scCO2

170

(1)

Polymer synthesis in scCO2

171

(1)

Suzuki-Miyaura reaction in scCO2

172

(1)

Continuous etherification in scCO2

172

(1)

Enzymatic reaction in scCO2

173

(1)

Photochemical reaction in scCO2

173

(1)

Hydrogenation of styrene in an scCO2/H2O emulsion

174

(1)

Hydroformylation in scCO2/H2O

175

(1)

Hydroformylation in an scCO2/IL biphasic system using a continuous flow reactor

175

(1)

Hydrogenation of 1-butene in scCO2 using a membrane reactor

176

(1)

Catalyst/product separation for cyclic carbonate synthesis from scCO2

177

(1)

References

178

(5)

Index

183

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