Provides comprehensive coverage of the atom-economic approach to functionalized molecules using unsaturated hydrocarbons as starting materials

Unsaturated hydrocarbons have emerged as an important class of fundamental starting materials in organic synthesis. Synthetic methodologies incorporating unsaturated hydrocarbons continue to expand due to their numerous applications in the synthesis of a vast array of chemicals.

Addition Reactions with Unsaturated Hydrocarbons presents an up-to-date overview of modern methods that utilize reactions of unsaturated hydrocarbons as building blocks of organic synthesis, covering the conceptual and practical knowledge required for designing atom-efficient reactions to synthesize functionalized molecules. This authoritative volume discusses homo-dimerization and cross-dimerization of alkynes and/or alkenes, synthesis of carbonyl compounds from the hydration of alkynes, cycloadditions of alkynes and alkenes for the synthesis of carbocycles and heterocycles, double functionalization of alkynes and alkenes by addition reactions of element-element bonds, and more.Summarizes the most recent developments in the reactions of unsaturated hydrocarbonsFeatures more than 600 schemes describing typical reactions starting from unsaturated hydrocarbonsCovers topics such as alkynylated reactions, addition and cycloaddition reactions of alkynes and alkenes, and carbonylation of alkynes and alkenes with carbon monoxideIncludes examples of synthesis procedures of natural products involving alkyne transformation

With comprehensive coverage of important reactions of unsaturated hydrocarbons,Addition Reactions with Unsaturated Hydrocarbons is a valuable resource for organic chemists, pharmaceutical chemists, and biochemists in both academia and industry as well as an excellent reference text for graduate students in relevant areas of chemistry.

Ruimao Hua is Professor of Chemistry, Department of Chemistry, Tsinghua University, China. His research interests focus on organic synthetic methodologies from alkynes, organic materials for liquid crystal display and organic light emitting diode (OLED) displays.

Preface ix

Acknowledgments xv

Abbreviations xvii

1 Dimerization of Alkynes and Alkenes 1

1.1 Markovnikov Dimerization of Terminal Alkynes 1

1.2 Anti-Markovnikov (Head-to-Head) Dimerization of Terminal Alkynes 7

1.3 Dimerization and Cross-dimerization of Terminal Alkenes 14

1.4 Cross-dimerization of Different Alkynes or Alkynes with Alkenes 18

References 26

2 Addition of C(sp)H Bonds to Unsaturated Compounds 33

2.1 Addition of Terminal Alkynes to Carbonyl Compounds 33

2.2 Addition of Terminal Alkynes to Alkenes 36

2.3 Addition of Terminal Alkynes to Imines 38

2.4 Addition of Terminal Alkynes to Other Compounds 40

References 42

3 Functionalized Alkenes from Hydrofunctionalization of Alkynes 47

3.1 Hydroborations of Alkynes 47

3.2 Hydrosilylation of Alkynes 52

3.3 Hydrostannation of Alkynes 57

3.4 Hydroamination of Alkynes 61

3.4.1 Hydroamination of Alkynes with Primary Amines 61

3.4.2 Hydroamination of Alkynes with Secondary Amines 63

3.4.3 Cyclohydroamination of Alkynes 65

3.4.4 Aminocarbonylation of Alkynes 67

3.5 Hydrophosphination of Alkynes and Related HP(O) Addition 69

3.5.1 Hydrophosphination of Alkynes 70

3.5.2 Addition of PV(O)H Bond to Alkynes 72

3.6 Hydrothiolation of Alkynes 76

3.6.1 Markovnikov Hydrothiolation of Alkynes 77

3.6.2 Anti-Markovnikov Hydrothiolation of Alkynes 78

3.7 Addition of O-nucleophiles to Alkynes 81

3.7.1 Addition of Alcohols and Phenols to Alkynes 81

3.7.2 Addition of Acids to Alkynes 84

References 86

4 Hydrofunctionalization of CarbonCarbon Double Bonds 103

4.1 Hydroboration of Alkenes 103

4.1.1 Markovnikov Hydroboration of Alkenes 104

4.1.2 Anti-Markovnikov Hydroboration of Alkenes 104

4.1.3 Hydroboration of Allenes and 1,3-dienes 105

4.1.4 Asymmetric Hydroboration of Alkenes 106

4.2 Hydrosilylation of CarbonCarbon Double Bonds 107

4.2.1 Markovnikov and Anti-Markovnikov Hydrosilylation of Alkenes 107

4.2.2 Hydrosilylation of Allenes 109

4.2.3 Hydrosilylation of 1,3-dienes 110

4.2.4 Asymmetric Hydrosilylation of Alkenes 110

4.3 Hydrostannation of CarbonCarbon Double Bonds 111

4.4 Hydroamination of CarbonCarbon Double Bonds 113

4.4.1 Markovnikov Hydroamination of Alkenes 113

4.4.2 Anti-Markovnikov Hydroamination of Alkenes 115

4.4.3 Hydroamination of Allenes and 1,3-dienes 116

4.4.4 Asymmetric Hydroamination of Alkenes 118

4.4.5 Nitrogen Heterocycles from Intramolecular Hydroamination of Alkenes 119

4.5 Hydrophosphination of Alkenes and Related PV(O)H Addition 121

4.6 Hydrothiolation of CarbonCarbon Double Bonds 125

4.7 Addition of O-nucleophiles to Alkenes 128

References 130

5 Double Functionalization of Alkynes and Alkenes by Addition of ElementElement Bonds 147

5.1 Addition Reaction of Group 13 ElementElement Bonds 147

5.1.1 cis-Addition Reactions to Alkynes 147

5.1.2 trans-Addition Reactions to Alkynes 149

5.1.3 Addition Reactions to Alkenes 150

5.1.4 Synthesis of 1,1-diborylalkanes/Alkenes via Addition of BB Bond 151

5.2 Addition Reaction of Group 14 ElementElement Bonds 153

5.3 Addition Reaction of Group 15 ElementElement Bond 156

5.4 Addition Reactions of Group 16 ElementElement Bond 159

5.4.1 cis-Addition Reactions to Alkynes 160

5.4.2 trans-Addition Reactions to Alkynes 161

5.4.3 Different Heteroatom Bond Addition Reactions to Alkynes 163

5.4.4 Addition Reactions to Alkenes 163

5.5 Addition Reactions of ElementElement Bonds from Different Group Heteroatoms 164

5.5.1 cis-Addition Reactions to Alkynes 165

5.5.2 trans-Addition Reactions to Alkynes 169

5.5.3 Addition Reactions to Alkenes 172

References 174

6 Double Functionalization of Alkynes by Addition of CarbonElement Bonds 183

6.1 Addition Reactions of CarbonGroup 13 Bonds 183

6.2 Addition Reactions of CarbonGroup 14 Bonds 185

6.2.1 Addition Reactions of CarbonSilicon Bonds 185

6.2.2 Addition Reactions of CarbonGermanium Bonds 188

6.2.3 Addition Reactions of CarbonTin Bonds 189

6.3 Addition Reactions of CarbonGroup 15 Bonds 191

6.4 Addition Reactions of CarbonGroup 16 Bonds 195

6.4.1 Addition Reactions of CarbonOxygen Bonds 195

6.4.2 Addition Reaction of CarbonSulfur Bonds 198

6.4.3 Addition Reactions of CarbonSelenium Bonds 202

6.5 Addition Reactions of CarbonHalogen Bonds to Alkynes 204

6.5.1 C(sp3)X Activation and Its Addition Reactions 205

6.5.2 C(sp2)X Activation and Its Addition Reactions 208

6.5.3 C(sp)X Activation and Its Addition Reactions 213

6.6 Addition Reactions of CarbonCarbon Single Bonds 216

6.6.1 Addition Reactions of Strained CC Bonds 216

6.6.2 Addition Reactions of CCN Bonds 218

6.6.3 Other CarbonCarbon Bond Cleavage and Their Addition Reactions 222

References 224

7 Carbocycles from Annulation of Alkynes and Alkenes 235

7.1 Four-Membered Carbocycles 235

7.1.1 Construction of Cyclobutenes 235

7.1.2 Construction of Cyclobutanes 240

7.2 Five-Membered Carbocycles 242

7.2.1 Five-Membered Carbocycles by [2+2+1] Cycloaddition 242

7.2.2 Five-Membered Carbocycles by [3+2] Cycloaddition 243

7.2.3 Intramolecular Cycloaddition of Active sp3 CH to CarbonCarbon Unsaturated Bonds 248

7.2.4 Five-Membered Carbocycles from Intramolecular Cycloaddition of Unsaturated Bonds 250

7.3 Six-Membered Carbocycles 251

7.3.1 Benzene Ring Formation 251

7.3.2 Naphthalene and Polyaromatic Hydrocarbons (PAHs) Ring Formation 258

7.3.3 1,3-Cyclohexadiene Ring Formation Via Cycloaddition of Alkynes 263

7.4 Seven-Membered Carbocycles 266

7.5 Eight-Membered and Larger Carbocycles 268

References 272

8 Heterocycles from Cycloaddition of Alkynes 285

8.1 Four-membered Heterocycles 285

8.2 Five-membered Heterocycles 286

8.2.1 Pyrroles, Furans, and Thiophenes Synthesis 287

8.2.2 Indoles, Benzo[b]Furans, Benzo[b]Thiophenes, and Benzo[b]Selenophenes 300

8.2.3 Five-membered Rings with Two Heteroatoms 308

8.3 Six-membered Heterocycles 319

8.3.1 Pyridine Derivatives via Cycloaddition of Alkynes with Nitriles 320

8.3.2 Benzopyridine Derivatives (Quinolines and Isoquinolines) 326

8.3.3 2-Pyridone Derivatives and Their Benzo-derivatives (Quinolinones and Isoquinolonones) 330

8.3.4 Six-membered N-heterocycles Having Two Nitrogen Atoms 334

8.3.5 2-Pyrone, Coumarin, Isocoumarin, and Chromone Derivatives 336

8.4 Other Heterocycles 341

References 346

9 Carbonyl Compounds from Alkynes and Alkenes 365

9.1 Hydration of Alkynes 365

9.2 Hydroformylation of Alkynes and Alkenes 369

9.2.1 Hydroformylation of Alkynes 369

9.2.2 Hydroformylation of Alkenes 370

9.3 Hydroacylation of Alkynes and Alkenes 372

9.4 Hydroamidation of Alkynes and Alkenes 376

9.5 Hydrocarboxylation of Alkynes and Alkenes 378

9.6 Hydroesterification of Alkynes and Alkenes 379

9.7 Carbonylation of Alkynes and Alkenes 380

9.7.1 Carbonylation of Alkynes 381

9.7.2 Carbonylation of Alkenes 384

9.7.3 Cyclocarbonylation of Alkynes and/or Alkenes 384

References 393

10 Natural Product Synthesis via Alkyne Transformation 407

10.1 Hydrofunctionalization of Alkynes in Natural Product Synthesis 407

10.2 Double Functionalization of Alkynes in Natural Product Synthesis 408

10.3 Cycloaddition of Alkynes in Natural Product Synthesis 408

10.4 Carbonylation of Alkynes in Natural Product Synthesis 411

References 412

Index 415