Comprehensive Organic Reactions in Aqueous Media

Chao-Jun Li, PhD, is Professor at McGill University in Canada. Professor Li began teaching at Tulane University in 1994 and received an NSF CAREER Award for work done from 1998–2002, the Outstanding Young Oversea Scientist Award from the NSFC in 2001, and the U.S. Presidential Green Chemistry Challenge Award in Academia for 2001. Dr. Li moved to McGill University in 2003 and received a Canada Research Chair in Green Chemistry (Tier I). He coauthored the popular first edition of Organic Reactions in Aqueous Media (Wiley). Tak-Hang Chan, PhD, is Professor Emeritus at McGill University in Canada and Chair Professor of Organic Chemistry at the Hong Kong Polytechnic University in Hong Kong. In 1993, Professor Chan received the prestigious R.U. Lemieux Award of the Canadian Society of Chemistry. A pioneer in green chemistry, he is a Fellow of the Royal Society of Canada and holds Honorary Professorships at Academia Sinica, Peking University, and Lanzhou University. He was coauthor of the first edition.

• Preface to the Second Edition xv1 Introduction 11.1 The Structure and Forms of Water 31.2 Properties of Water 41.3 Solvation 61.4 Hydrophobic Effect 61.5 Salt Effect 81.6 Water Under Extreme Conditions 9References 132 Alkanes 152.1 Oxygenation of Alkanes 152.2 Halogenation of Alkanes 202.3 Formation of Carbon–Carbon Bonds 202.4 DH Exchange of Alkanes in Water 21References 223 Alkenes 253.1 Reduction 253.1.1 Hydrogenation 253.2 Electrophilic Additions 283.2.1 Reaction with Halogen 283.2.2 Reaction with Hydrogen Halides 283.2.3 Addition of Water 293.2.4 OxymercurationOxymetalation 293.2.5 Epoxidation 303.2.6 Dihydroxylation and Hydroxylamination 353.2.7 Wacker’s Oxidation 403.2.8 Oxidative C=C Bond Cleavage 433.2.9 C–C Bond Formations 463.3 Radical Reactions of Alkenes 473.3.1 Radical Polymerization of Alkenes 473.3.2 Radical Additions 483.3.3 Radical Cyclization 493.4 Carbene Reactions 503.4.1 The Generation of Carbenes in Aqueous Medium 503.4.2 The Stability of Carbenes 503.4.3 The Reaction of Carbenes with Alkenes in Aqueous Medium 513.5 Alkene Isomerization 523.6 Transition-Metal Catalyzed C–C Formation Reactions 533.6.1 Polymerizations 533.6.2 Heck Reactions and Related VinylationArylation 543.6.3 Hydrovinylation 563.6.4 Reaction with Arenes 563.6.5 Hydroformylation 573.6.6 Reaction with Alkynes 583.6.7 Carbonylation 603.6.8 Cycloaddition Reactions of Alkenes 603.7 Olefin Metathesis 603.7.1 Ring-Opening Metathesis Polymerization (romp) 613.7.2 Ring-Closing Metathesis (RCM) 623.8 Reaction of Allylic C–H Bond 643.8.1 Allylic Oxidation 643.8.2 C–C Bond Formations 65References 664 Alkynes 774.1 Reaction of Terminal Alkynes 774.1.1 Alkyne Oxidative Dimerization 774.1.2 Alkyne-Alkyne Addition 784.1.3 Reaction of Alkynes with Organic Halides 814.1.4 Reaction of Alkynes with Carbonyl Compounds 934.1.5 Reaction of Alkynes with C=N Compounds 944.1.6 Conjugate Addition with Terminal Alkynes 974.2 Additions of C≡C bonds 984.2.1 Reduction  984.2.2 Addition of Water 984.2.3 Addition of Alcohols and Amines 1004.2.4 Hydrosilation and Hydrometalations 1024.2.5 Addition of Aryls 1044.2.6 Carbonylation of Internal Alkynes 1074.2.7 Other Additions to Alkynes 1094.3 Transition-Metal Catalyzed Cycloadditions 1094.3.1 Pauson-Khand-Type Reactions 1094.3.2 [2 + 2 + 2] Cyclotrimerization 1114.3.3 [2 + 2 + 2] Alkyne-Nitrile Cyclotrimerization 1144.3.4 [3 + 2] 1,3-Dipolar Cycloaddition  1144.3.5 [4 + 2] Cycloaddition 1184.3.6 [5 + 2] Cycloaddition 1194.3.7 Other Cycloadditions 1194.4 Other Reactions 121References 1215 Alcohols, Phenols, Ethers, Thiols, and Thioethers 1295.1 Oxidation of Alcohols 1295.1.1 Diol Cleavage 1345.2 SubstitutionsElimination 1345.3 Addition of Alcohols, Phenols, and Thiols to Alkene and Alkyne Bonds 1375.4 Addition of Alcohols to C=O Bonds: Esterification and Acetal Formations 1375.5 Reaction of Ethers and Cyclic Ethers 1385.5.1 Ethers and Cyclic Ethers 1385.5.2 Reactions of Epoxides in Water and “Click Chemistry” 1395.6 Reaction of Sulfur Compounds 1415.6.1 Oxidation of Thiols and Thioethers 1415.6.2 Reduction of Disulfides 1425.6.3 Native Chemical Ligation for Peptide Synthesis 1435.6.4 Other Reactions 143References 1446 Organic Halides 1516.1 General 1516.2 Reduction 1516.3 Elimination Reactions 1546.4 Nucleophilic Substitutions 1546.4.1 Substituted by Heteroatoms 1546.4.2 Carbon–Carbon Bond Formations 1586.5 Reductive Coupling 1616.5.1 Wurtz-Type Coupling 1616.5.2 Ullmann-Type Coupling and Related Reactions 1636.6 Carbonylation of Organic Halides 1646.6.1 Carbonylation of Alkyl Halides 1646.6.2 Carbonylation of Allylic and Benzylic Halides 1656.6.3 Carbonylation of Aryl Halides 1656.7 Transition-Metal Catalyzed Coupling Reactions 1666.7.1 The Heck Coupling 1666.7.2 The Suzuki Coupling 1676.7.3 The Stille Coupling 1726.7.4 Other Transition-Metal Catalyzed Couplings 173References 1747 Aromatic Compounds 1817.1 General 1817.2 Substitution Reactions 1827.2.1 Electrophilic Substitutions 1827.2.2 Friedel-Crafts C–C Bond Formations 1837.2.3 Other Substitution Reactions 1897.3 Oxidation Reactions 1907.3.1 Simple Oxidation 1907.3.2 Oxidative Coupling 1917.4 Reductions 192References 1938 Aldehdye and Ketones 1978.1 Reduction 1978.1.1 Hydrogenation 1978.1.2 Other Reductions 1988.2 Oxidation 2048.3 Nucleophilic Addition: C–C Bond Formation 2068.3.1 Allylation 2068.3.2 Propargylation 2388.3.3 Cyclopentadienylation 2428.3.4 Benzylation 2428.3.5 ArylationVinylation 2448.3.6 Alkynylation 2468.3.7 Alkylation  2468.3.8 Reformatsky-Type Reaction 2468.3.9 Direct Aldol Reaction 2488.3.10 Mukaiyama Aldol Reaction 2528.3.11 Hydrogen Cyanide Addition 2588.3.12 Wittig Reactions 2598.4 Pinacol Coupling 2618.5 Other Reactions (Halogenation and Oxidation of α-H) 262References 2639 Carboxylic Acids and Derivatives 2799.1 General 2799.1.1 Reaction of α-Hydrogen 2799.1.2 Reduction 2799.2 Carboxylic Acids 2809.2.1 EsterificationAmidation 2809.2.2 Decarboxylation 2879.3 Carboxylic Acid Derivatives 2879.3.1 Esters and Thiol Esters 2879.3.2 Acid Halides and Anhydrides 2889.3.3 Amides 2899.3.4 Nitriles 289References 29010 Conjugated Carbonyl Compounds 29310.1 Reduction 29310.1.1 Hydrogenation 29310.1.2 Asymmetric Hydrogenation 29510.1.3 Reduction by Other Methods 29610.2 Epoxidation, Dihydroxylation, Hydroxyamination 29710.3 Conjugate Addition: Heteroatom 29810.4 C–C Bond Formation 30110.4.1 Addition of Hydrogen Cyanide 30210.4.2 Addition of α-Carbonyl Compounds 30210.4.3 Addition of Allyl Groups 30410.4.4 Addition of Alkyl Groups 30510.4.5 Addition of Vinyl and Aryl Groups 30710.4.6 Addition of Alkynyl Groups 31010.4.7 Other Conjugate Additions 31010.5 Other Reactions 31010.5.1 Reductive Coupling 31010.5.2 Baylis-Hillman Reactions 31110.5.3 γ-Addition of Alkynoates 314References 31511 Nitrogen Compounds 32111.1 Amines 32111.1.1 Alkylation 32111.1.2 Diazotization and Nitrosation 32211.1.3 Oxidation 32311.1.4 Reaction with Carbonyl Compounds 32611.2 Imines 32711.2.1 Reductions 32711.2.2 Nucleophilic Additions 32911.2.3 Reductive Coupling 34211.3 Diazo Compounds 34311.3.1 Substitution 34311.3.2 Reduction 34311.3.3 Cyclopropanation 34411.3.4 Coupling Reaction 34611.4 Azides 34611.4.1 Substitution 34611.4.2 Click Chemistry 34711.5 Nitro Compounds 349References 34912 Pericyclic Reactions 35512.1 Introduction 35512.2 Diels-Alder Reactions 35712.2.1 Lewis-Acid Catalysis 36012.2.2 Asymmetric Diels-Alder Reactions 36712.2.3 Theoretical and Mechanistic Studies 37112.2.4 Synthetic Applications 37412.2.5 Hetero-Diels-Alder Reactions 38212.2.6 Asymmetric Hetero-Diels-Alder Reactions 38812.2.7 Other Cyclization Reactions 39012.3 Sigmatropic Rearrangements 39212.3.1 Claisen Rearrangements 39212.3.2 Cope Rearrangements 39712.4 Photochemical Cycloaddition Reactions 398References 399Index 409

"As it is a conference report, the book is clearly intended for specialists in the field." (Angewandte Chemie, 2008-47/11) "…a testament to the enormous expansion in the field of water-based chemistry, and compiling it in a single volume is very useful." (Journal of the American Chemical Society, December 26, 2007)"Advanced students and research and development chemists with an interest in green chemistry are highly recommended to purchase this book." (Organic Chemistry Portal, January 2008)