<p>List of Contributors xiii</p> <p><b>1 The Applications ofWater as Reagents in Organic Synthesis 1<br /></b><i>Zhengkai Chen and Hongjun Ren</i></p> <p>1.1 Introduction 1</p> <p>1.2 Incorporation of Hydrogen Atom from theWater 2</p> <p>1.2.1 1,2,3-Triazoles 4</p> <p>1.3 Incorporation of Oxygen Atom from theWater 7</p> <p>1.4 Incorporation of Hydroxyl Group fromWater 31</p> <p>1.5 Traceless Promotion of the Reactions byWater 39</p> <p>1.6 Conclusions 44</p> <p>References 44</p> <p><b>2 The Applications of Toluene and Xylenes 49<br /></b><i>Krishna Nand Singh, Narendra R. Chaubey, and Neetu Singh</i></p> <p>2.1 Application of Toluene and Xylenes as Reagents 50</p> <p>2.2 Oxidation of Methyl Group into Common Functionalities 50</p> <p>2.3 Application of Methyl Group as Acyl Building Block 51</p> <p>2.3.1 Synthesis of Carbonyl Compounds 51</p> <p>2.3.2 Synthesis of Amides 53</p> <p>2.3.3 Synthesis of N-Aroyl Sulfoximines 54</p> <p>2.3.4 Synthesis of Esters 55</p> <p>2.3.5 Synthesis of Thioesters 56</p> <p>2.4 Application as Alkyl Building Block 60</p> <p>2.4.1 Synthesis of Nitriles 60</p> <p>2.4.2 Synthesis of 2-Phenyl Acetic Acid Derivatives 61</p> <p>2.4.3 Alkylation of Sulfonamides 62</p> <p>2.4.4 Alkylation ofThiophenols 63</p> <p>2.4.5 Synthesis of Trifluoromethyl Sulfides 64</p> <p>2.4.6 Synthesis of Benzyl Esters 64</p> <p>2.4.7 Synthesis of Phosphate Esters 66</p> <p>2.4.8 Synthesis of Carbamates,Thioamides, and Esters 66</p> <p>2.4.9 Synthesis of 3-Benzyl Coumarin Derivatives 66</p> <p>2.4.10 Decarboxylative Benzylation of Cinnamic Acids 68</p> <p>2.4.11 Synthesis of Functionalized Oxindoles 68</p> <p>2.4.12 Synthesis of Dihydroquinolinones 69</p> <p>2.4.13 Benzylation of Enones 69</p> <p>2.4.14 Coupling with 1,3-Dicarbonyl Compounds 70</p> <p>2.4.15 Benzylation of Pyridine-N-Oxide 70</p> <p>2.4.16 Synthesis of Dihydrofurans 70</p> <p>2.4.17 Synthesis of Quinoline Derivatives 71</p> <p>2.4.18 Reaction with Ethyl Diazoacetate 72</p> <p>2.4.19 Synthesis of Benzo[b]phosphole Oxides 72</p> <p>2.4.20 Synthesis of β-Aromatic α-Amino Acid Derivatives 73</p> <p>2.4.21 Halogenation Reactions 73</p> <p>2.4.22 N-Benzylation of Isoquinolines 75</p> <p>2.5 Application as Esters Building Block 76</p> <p>2.6 Application as Alcohols Building Block 77</p> <p>References 77</p> <p><b>3 The Applications of 1,4-Dioxane, THF, and Ethers as Versatile Building Blocks in Organic Synthesis 81<br /></b><i>Ping Liu, Guanghui Zhang, and Peipei Sun</i></p> <p>3.1 Introduction 81</p> <p>3.2 Cleavage of C(sp3)–H of Ethers 82</p> <p>3.2.1 Cross-Dehydrogenative Coupling Reactions of Ethers 82</p> <p>3.2.1.1 C–C Bond Formation 83</p> <p>3.2.1.2 C–N Bond Formation 91</p> <p>3.2.1.3 C–O Bond Formation 93</p> <p>3.2.2 The Formation of C–S Bond 97</p> <p>3.2.3 Addition of Ethers to C=C and C≡C Bonds 98</p> <p>3.2.4 Decarboxylative Alkenylation or Alkylation Reactions 104</p> <p>3.2.5 Radical Alkenylation and Alkynylation of Ethers 106</p> <p>3.2.6 Radical α-C–H Hydroxyalkylation and Aminoalkylation of Ethers 107</p> <p>3.2.7 Intermolecular Carbenoid Insertion to α-C–H Bond of Ethers 109</p> <p>3.2.8 C(sp3)–H Arylation with Arylmetal or Arylboron Reagents 109</p> <p>3.3 Cleavage of C–O of Ethers 112</p> <p>3.4 Cleavage of C–C Bonds of Ethers 117</p> <p>3.5 Conclusion 118</p> <p>References 118</p> <p><b>4 The Application of Dichloromethane and Chloroform as Reagents in Organic Synthesis 125<br /></b><i>Anis Tlili and Johannes Schranck</i></p> <p>4.1 The Application of Dichloromethane and Chloroform as Reagents in Organic Synthesis 125</p> <p>4.1.1 Dichloromethane 125</p> <p>4.1.1.1 Reactions of Dichloromethane with Posttransition Metals 126</p> <p>4.1.1.2 Reactions of Dichloromethane with Transition Metals 127</p> <p>4.1.1.3 Reactions of Dichloromethane with Phosphines 135</p> <p>4.1.1.4 Reactions of Dichloromethane with Amines and Phosphines 136</p> <p>4.1.1.5 Reactions of Dichloromethane with Amines 136</p> <p>4.1.1.6 Reactions of Dichloromethane with Amines and Nucleophilic Carbon Derivatives 139</p> <p>4.1.1.7 Reaction of Dichloromethane with Nucleophilic Sulfur 141</p> <p>4.1.2 Chloroform 142</p> <p>4.1.2.1 Reaction of Chloroform with Hydrogen Fluoride 142</p> <p>4.1.2.2 Reactions of Chloroform with Post-TransitionMetals 142</p> <p>4.1.2.3 Reactions of Chloroform with Transition Metals 143</p> <p>4.1.2.4 Formation and Use of Dichlorocarbene 146</p> <p>References 154</p> <p><b>5 The Applications of Acetone and Ethyl Acetates 161<br /></b><i>Jie-PingWan</i></p> <p>5.1 Acetone 161</p> <p>5.1.1 Aldol Reaction 161</p> <p>5.1.2 Claisen–Schmidt Reaction 167</p> <p>5.1.3 Mannich Reaction 170</p> <p>5.1.4 Miscellaneous 175</p> <p>5.2 Ethyl Acetate 182</p> <p>5.2.1 Transesterification 183</p> <p>5.2.2 Amidation 187</p> <p>5.2.3 Miscellaneous 190</p> <p>References 192</p> <p><b>6 N,N-Dimethylformamide and N,N-Dimethylacetamide as Carbon, Hydrogen, Nitrogen, and/or Oxygen Sources 199<br /></b><i>Jean Le Bras and Jacques Muzart</i></p> <p>6.1 Introduction 199</p> <p>6.2 Amination 200</p> <p>6.2.1 Benzylic and (Hetero)aryl Halides 200</p> <p>6.2.2 Benzyl and Allyl Acetates 205</p> <p>6.2.3 Ketones and Aldehydes 206</p> <p>6.2.4 Azoles 207</p> <p>6.2.5 Others 208</p> <p>6.3 Amidation andThioamidation 209</p> <p>6.3.1 Using the DM DimethylamineMoiety 209</p> <p>6.3.1.1 Aryl and Alkenyl Halides or Triflates 209</p> <p>6.3.1.2 Acyl Halides 210</p> <p>6.3.1.3 Carboxylic Acids, α-Ketoacids, Esters, Peresters, and Anhydrides 211</p> <p>6.3.1.4 Primary Alcohols and Aldehydes 216</p> <p>6.3.1.5 Methyl Ketones 217</p> <p>6.3.1.6 Nitriles 218</p> <p>6.3.1.7 Dibenzyldisulfanes 219</p> <p>6.3.2 Using the DM DimethylcarbamoylMoiety 219</p> <p>6.3.2.1 Aryl Halides 219</p> <p>6.3.2.2 Ketones 221</p> <p>Compounds 221</p> <p>6.3.2.4 Phenols 221</p> <p>6.3.2.5 Thiophenols 223</p> <p>6.3.2.6 Alkenes 223</p> <p>6.3.2.7 Alkynes 223</p> <p>6.3.2.8 Amines 224</p> <p>6.3.2.9 Amides 225</p> <p>6.3.2.10 Nitriles 225</p> <p>6.3.2.11 Isonitriles 226</p> <p>6.3.2.12 Benzothiazoles 226</p> <p>6.3.2.13 Selenides and Sulfides 226</p> <p>6.3.2.14 Aryl-Tethered Activated Alkenes 227</p> <p>6.3.3 Using the DM Formyl/Acetyl Moiety 227</p> <p>6.3.4 Using the DMF Dimethylamino-CarbonMoiety 231</p> <p>6.3.5 Using CH, CHCONMe2, CH2CONMe2, or H(Me)CONMeCH2 Moiety of DM 233</p> <p>6.3.5.1 Alcohols 233</p> <p>6.3.5.2 Aldehydes and Ketones 234</p> <p>6.3.5.3 Carboxylic Acids and α-Ketoacids 235</p> <p>6.3.5.4 Amines 235</p> <p>6.3.5.5 Imides and Amides 236</p> <p>6.3.5.6 Alkenes 237</p> <p>6.3.5.7 Sulfides 237</p> <p>6.3.5.8 (Hetero)arenes 238</p> <p>6.3.5.9 Domino Reactions 240</p> <p>6.4 Amidination 241</p> <p>6.4.1 Sulfonamides 241</p> <p>6.4.2 Enamines 242</p> <p>6.5 Formylation and Related Domino Reactions 242</p> <p>6.5.1 Vilsmeier-Mediated Formylations 243</p> <p>6.5.1.1 (Hetero)arenes 243</p> <p>6.5.1.2 Alkenes 245</p> <p>6.5.1.3 O-Silylated Ethers 246</p> <p>6.5.1.4 Alcohols and Phenols 246</p> <p>6.5.1.5 Enamines 247</p> <p>6.5.1.6 Activated Methyl Groups 247</p> <p>6.5.2 VR-Mediated Domino Reactions 247</p> <p>6.5.2.1 Formylation and Cyclization 247</p> <p>6.5.2.2 Haloformylation 249</p> <p>6.5.2.3 Haloformylation and Cyclization 250</p> <p>6.5.2.4 Ring Opening, Haloformylation, and Cyclization 252</p> <p>6.5.2.5 Diformylation 253</p> <p>6.5.2.6 Intramolecular Formylation-Intermediate Trapping 254</p> <p>6.5.3 Using Organolithiens or Organomagnesiens 256</p> <p>6.5.4 Hydroformylation 258</p> <p>6.5.5 Formoxylation 259</p> <p>6.6 Carbonylation 260</p> <p>6.6.1 Carbonyl from DMF 260</p> <p>6.6.2 Carbon from DM DimethylamineMoiety 262</p> <p>6.7 Cyanation 264</p> <p>6.7.1 Carbon from DMF Carbonyl 264</p> <p>6.7.1.1 Vilsmeier Procedure 264</p> <p>6.7.1.2 n-BuLi (or Mg)/I2/NH3 Procedure 265</p> <p>6.7.2 Carbon from DM Dimethyl 266</p> <p>6.7.2.1 Pd/Cu Procedure 266</p> <p>6.7.2.2 Cu Procedure 267</p> <p>6.7.3 Carbon and Nitrogen from DM Dimethyl 269</p> <p>6.7.3.1 Pd Procedure 269</p> <p>6.7.3.2 Cu Procedure 270</p> <p>6.8 Insertion Reactions 271</p> <p>6.8.1 Alkenes 271</p> <p>6.8.2 Alkynes 272</p> <p>6.8.3 Arynes 274</p> <p>6.8.4 Imines 276</p> <p>6.8.5 Carbenes 276</p> <p>6.8.6 Nitriles 278</p> <p>6.9 Miscellaneous Reactions 278</p> <p>6.9.1 Cycloaddition 278</p> <p>6.9.2 Methylenation 278</p> <p>6.9.2.1 Of Benzylic Carbons 278</p> <p>6.9.2.2 Of Aromatic Carbons 280</p> <p>6.9.2.3 Of Enolic Carbons 282</p> <p>6.9.3 Methylidynation 283</p> <p>6.9.4 Acetylation 285</p> <p>6.9.5 Ether Formation 285</p> <p>6.9.6 Anhydride Formation 286</p> <p>6.9.7 Substitution 286</p> <p>6.9.8 Hydrogen Delivery 289</p> <p>6.9.9 Acetalization of DMF 294</p> <p>6.9.10 Thionation of DM 294</p> <p>6.9.11 Hydrodeoxygenation of DMF 294</p> <p>Acknowledgments 295</p> <p>References 296</p> <p><b>7 The Applications of DMSO 315<br /></b><i>Jia-Chen Xiang, Qing-He Gao, and An-XinWu</i></p> <p>7.1 A Brief Introduction of DMSO 315</p> <p>7.2 Name Reactions 316</p> <p>7.2.1 Swern Oxidation 316</p> <p>7.2.2 Parikh–Doering Oxidation 316</p> <p>7.2.3 Pfitzner–Moffatt Oxidation 317</p> <p>7.2.4 Kornblum Oxidation 317</p> <p>7.3 As Reaction Reagents 318</p> <p>7.3.1 Providing –OH (Hydroxylation Reagent) 318</p> <p>7.3.2 Providing –CO (Carbonylation Reagent) 320</p> <p>7.3.3 Providing –SO2Me (Sulfonylation Reagent) 321</p> <p>7.3.4 DMSO Serves as a Source of Sulfur 324</p> <p>7.3.4.1 Providing –MeSMe Group 324</p> <p>7.3.4.2 Providing –SMe Group 326</p> <p>7.3.4.3 Providing –SOMe Group 331</p> <p>7.3.5 As One-Carbon Synthon 332</p> <p>7.3.5.1 Methylation Reagent 332</p> <p>7.3.5.2 Formylation Reagent 332</p> <p>7.3.5.3 Cyanation Reagent 335</p> <p>7.3.5.4 One-Carbon Unit to Participate in the Ring or Bridge Formation 336</p> <p>7.3.6 Dimsyl Anion Activation Reagent 339</p> <p>7.4 As Multifunctional Catalyst/Reagent in Self-Sorting Reaction</p> <p>System 342</p> <p>7.5 Summary and Perspectives 349</p> <p>Acknowledgments 349</p> <p>References 349</p> <p><b>8 Acetonitrile as Reagents in Organic Synthesis: Reactions and Applications 355<br /></b><i>Shun-YiWang, Xue-Qiang Chu, Yi Fang, and Shun-Jun Ji</i></p> <p>8.1 Introduction 355</p> <p>8.2 Transition-Metal-Catalyzed Cross-Coupling of Acetonitrile and</p> <p>Nitriles 355</p> <p>8.3 Free-Radical-Initiated C–H Functionalization of Acetonitrile and Nitriles 364</p> <p>8.4 Summary and Outlook 374</p> <p>Acknowledgments 374</p> <p>References 374</p> <p><b>9 The Applications of Nitromethane as Reagent and Solvent in Organic Synthesis 377<br /></b><i>Xinxin Qi, Jin-Bao Peng, and Xiao-FengWu</i></p> <p>9.1 Introduction 377</p> <p>9.2 Reactions with Aldehydes 377</p> <p>9.3 Reactions with Imines 385</p> <p>9.4 Reactions with Ketones 387</p> <p>9.5 Michael Reaction 388</p> <p>9.6 Other Reactions 391</p> <p>References 395</p> <p><b>10 Alcohol as a Reagent in Homogeneous Catalysis 403<br /></b><i>Feng Han,Wei Sun, Chungu Xia, and Chao Liu</i></p> <p>10.1 Introduction 403</p> <p>10.2 Alcohol as O-nucleophile 403</p> <p>10.2.1 Esterification Reaction 403</p> <p>10.2.2 Oxa-Michael Addition 411</p> <p>10.2.3 Etherification of Alcohol 414</p> <p>10.2.3.1 Etherification of Alcohol with Halide 414</p> <p>10.2.3.2 Etherification of Alcohol with C–H 418</p> <p>10.3 Alcohol Oxidation or α-C–H Functionalization (Alcohol as C-nucleophile) 421</p> <p>10.3.1 Oxidation 421</p> <p>10.3.2 α-C–H Functionalization 422</p> <p>10.4 Alcohol as Electrophile 424</p> <p>10.4.1 Amination (Amine as Nucleophilic Reagent) 424</p> <p>10.4.2 Alkylation Reaction with Alcohol (Alcohol as Electrophiles) 426</p> <p>10.4.2.1 Alcohol and Alkene 426</p> <p>10.4.2.2 Alcohol and Alkyne 428</p> <p>10.4.2.3 Alcohol and Indole 430</p> <p>10.4.2.4 Alcohol with Other Aromatic Systems 432</p> <p>10.4.3 Ritter Reaction of Alcohol and Nitrile 435</p> <p>10.4.3.1 Brønsted Acid Catalyst 435</p> <p>10.4.3.2 Lewis Acid and Metal Catalysis 436</p> <p>10.5 Conclusion 436</p> <p>References 437</p> <p><b>11 Synchronous Application of Hydrocarbons as Solvents and Reagents in Transition-Metal Catalysis 449<br /></b><i>Jian Cao and Li-Wen Xu</i></p> <p>11.1 Introduction 449</p> <p>11.2 Aromatic Hydrocarbons 449</p> <p>11.2.1 C–C Bond Formation 449</p> <p>11.2.1.1 Arene–Arene Coupling 449</p> <p>11.2.1.2 Arene–Alkene Coupling 458</p> <p>11.2.1.3 Arene–Alkyne Coupling 468</p> <p>11.2.1.4 Arene–Haloarenes Coupling 471</p> <p>11.2.1.5 Arene–Arylboronic Acid Coupling 476</p> <p>11.2.1.6 Arene–CO–Alcohol/Amine Coupling 477</p> <p>11.2.2 C–N Bond Formation 478</p> <p>11.2.3 C–O Bond Formation 482</p> <p>11.2.4 C–B Bond Formation 484</p> <p>11.2.5 C–Si Bond Formation 487</p> <p>11.3 Aliphatic Hydrocarbons 491</p> <p>11.3.1 C–C Bond Formation 491</p> <p>11.3.1.1 Alkane–Arene Coupling 491</p> <p>11.3.1.2 Alkane–Alkene Coupling 493</p> <p>11.3.1.3 Alkane-Alkyne Coupling 497</p> <p>11.3.1.4 Alkane–Ketone Coupling 497</p> <p>11.3.1.5 Alkane–Aldehyde Coupling 498</p> <p>11.3.1.6 Alkane–Isocyanide Coupling 499</p> <p>11.3.1.7 Alkane–CO–Amine Coupling 499</p> <p>11.3.1.8 Alkane–Carbene Coupling 500</p> <p>11.3.1.9 Alkane–Arylboronic Acid Coupling 501</p> <p>11.3.2 C–N Bond Formation 502</p> <p>11.3.3 C–O Bond Formation 504</p> <p>11.3.4 C–S Bond Formation 504</p> <p>11.3.5 C–B Bond Formation 506</p> <p>11.4 Conclusions 507</p> <p>Acknowledgments 507</p> <p>References 508</p> <p>Index 515</p>