Preface ........................................................ XI
List of Contributors ......................................... XVII
Part I Innovative Processes in Organic Chemistry ............... 1
1 N-Hydroxy Derivatives: Key Organocatalysts for the
Selective Free Radical Aerobic Oxidation of Organic
Compounds .................................................... 3
Carlo Punta and Cristian Gambarotti
1.1 Introduction ............................................ 3
1.2 General Reactivity of N-Hydroxy Derivatives ............. 3
1.3 Aerobic Oxidation Catalyzed by N- Hydroxy Amines ........ 6
1.3.1 Aerobic Oxidation of Alcohols to Aldehydes and
Ketones .......................................... 6
1.4 Aerobic Oxidation Catalyzed by N-Hydroxy Amides ......... 9
1.4.1 Peroxidation of Polyunsaturated Fatty Acids ...... 9
1.5 Aerobic Oxidation Catalyzed by N-Hydroxy Imides ........ 10
1.5.1 Oxidation of Benzylalcohols to Aldehydes ........ 10
1.5.2 Oxidation of Silanes ............................ 12
1.5.3 Oxidation of N-Alkylamides ...................... 12
1.5.4 Oxidation of Tertiary Benzylamines to
Aldehydes ....................................... 13
1.5.5 Oxidative Functionalization of Alkylaromatics ... 14
1.5.6 Oxidative Acylation of N-Heteroaromatic Bases ... 15
1.5.7 Aerobic Synthesis of p-Hydroxybenzoic Acids
and Diphenols ................................... 16
1.5.8 Selective Halogenation of Alkanes ............... 16
1.5.9 Aerobic Oxidation of Cycloalkanes to Diacids .... 17
1.5.10 Epoxidation of Olefins .......................... 18
1.5.11 Oxidation of Alkylaromatics ..................... 19
1.6 Conclusions ............................................ 20
Acknowledgments ........................................ 20
References ............................................. 21
2 Gold-Catalyzed Intra- and Intermolecular Cycloadditions of
Push-Pull Dienynes .......................................... 25
Manuel A. Fernández-Rodríguez
2.1 Introduction ........................................... 25
2.2 Gold-Catalyzed Enyne Cycloisomerizations ............... 26
2.2.1 General Remarks ................................. 26
2.2.2 Influence of the Electronic Nature of the
Alkyne Substituent .............................. 26
2.2.3 Gold-Catalyzed Cycloaromatization of Push-Pull
Dienyne Acids: Synthesis of 2,3-Disubstituted
Phenols ......................................... 29
2.3 Gold-Catalyzed Intermolecular Cycloadditions ........... 34
2.3.1 Cycloadditions of Enynes, Propargyl
Acetylenes, and Alkynyl Cyclopropanes ........... 34
2.3.2 Gold-Catalyzed Intermolecular Hetero-Dehydro-
Diels-Alder Cycloaddition of Push-Pull
Dienynes with Nonactivated Nitriles:
Regioselective Synthesis of Pyridines ........... 35
2.4 Conclusions and Future Perspectives .................... 40
Acknowledgments ........................................ 40
References ............................................. 41
3 N-Heterocyclic Carbenes in Copper-Catalyzed Reactions ....... 43
Silvia Díez-González
3.1 Introduction ........................................... 43
3.2 Preparation of NHC-Containing Copper Complexes ......... 43
3.3 Main Applications of [(NHC)Cu] Complexes in
Catalysis .............................................. 46
3.4 Copper Hydride-Mediated Reactions ...................... 49
3.4.1 Hydrosilylation of Carbonyl Compounds ........... 49
3.4.2 Mechanistic Considerations ...................... 51
3.4.3 Related Transformations ......................... 52
3.5 [3 + 2] Cycloaddition of Azides and Alkynes ............ 53
3.5.1 Click Chemistry ................................. 53
3.5.2 Use of Internal Alkynes: Mechanistic
Implications .................................... 55
3.6 Concluding Remarks ..................................... 57
Acknowledgments ........................................ 58
References ............................................. 58
4 Supported Organocatalysts as a Powerful Tool in Organic
Synthesis ................................................... 67
Francesco Giacalone, Michelangelo Gruttadauria, and Renato
Noto
4.1 Introduction ........................................... 67
4.2 L-Proline and its Derivatives on Ionic Liquid-
Modified Silica Gels ................................... 69
4.3 Polystyrene-Supported Proline as a Versatile and
Recyclable Organocatalyst .............................. 73
4.3.1 Nonasymmetric Reactions ......................... 75
4.3.1.1 α-Selenenylation of Aldehydes .......... 75
4.3.1.2 Baylis-Hillman Reaction ................ 77
4.3.2 Asymmetric Reactions ............................ 79
4.3.2.1 Aldol Reaction ......................... 79
4.4 Prolinamide-Supported Polystyrenes as Highly
Stereoselective and Recyclable Organocatalysts for
the Aldol Reaction ..................................... 82
4.5 Outlook and Future Perspectives ........................ 84
References ............................................. 85
5 The Complex-Induced Proximity Effect in Organolithium
Chemistry and Its Importance in the Lithiation of Tertiary
Amines ...................................................... 95
Viktoria H. Gessner
5.1 Introduction ........................................... 95
5.2 State of the Art ....................................... 96
5.2.1 Structure Formation Patterns of Organolithium
Compounds ....................................... 96
5.2.2 The Complex-Induced Proximity Effect (CIPE) ..... 97
5.2.3 Synthesis of α-Lithiated Tertiary Amines ........ 99
5.3 Latest Developments ................................... 101
5.3.1 Precoordination as Key to Direct
Deprotonation of Tertiary Amines ............... 101
5.3.2 Regioselective α -Lithiation ................... 104
5.3.3 α - Lithiation versus β - Lithiation ........... 108
5.4 Conclusions and Outlook ............................... 110
Acknowledgments ....................................... 111
References ............................................ 111
Part II Predictive Tools in Organic Chemical Reactions ....... 115
6 Double Hydrogen Bonding in Asymmetric Organocatalysis:
A Mechanistic Perspective .................................. 117
Tommaso Marcelli
6.1 Introduction .......................................... 117
6.2 Diols and Amidoalcohols ............................... 119
6.2.1 Single-Point versus Two-Point Activation ....... 119
6.2.2 The Impact of Acidity on Enantioselectivity .... 120
6.3 (Thio)ureas ........................................... 122
6.3.1 Mechanistic Duality in Aminothiourea
Catalysis ...................................... 122
6.3.2 Mono-versus Bidentate Coordination ............. 125
6.3.3 Catalyst Self-Association ...................... 126
6.3.4 Halide Binding ................................. 127
6.4 Phosphoric Acids ...................................... 129
6.4.1 Bifunctionality ................................ 130
6.4.2 Competent Substrates ........................... 133
6.5 Other Catalysts ....................................... 134
6.5.1 Guanidiniums ................................... 134
6.5.2 Squaramides .................................... 135
6.5.3 Quinolinium Thioamides ......................... 136
6.6 Conclusions and Outlook ............................... 137
References ............................................ 138
7 Dynamic Covalent Capture: A Sensitive Tool for Detecting
Molecular Interactions ..................................... 143
Leonard Prins
7.1 Introduction .......................................... 143
7.2 Hydrogen Bond-Driven Self-Assembly in Aqueous
Solution .............................................. 144
7.3 Measuring Stability and Order in Biological
Structures ............................................ 146
7.3.1 Peptides ....................................... 146
7.3.2 Bilayer Membranes .............................. 149
7.4 Drug Discovery ........................................ 150
7.5 Catalyst Discovery .................................... 152
7.6 The Analysis of Complex Chemical Systems .............. 156
7.6.1 1H-13C HSQC NMR Spectroscopy .................... 156
7.6.2 UV/Vis Spectroscopy ............................ 158
7.7 Perspective ........................................... 160
Acknowledgments ....................................... 162
References ............................................ 162
Part III Chemical Reactions, Sustainable Processes, and
Environment .......................................... 165
8 Furfural and Furfural-Based Industrial Chemicals ........... 167
Ana S. Dias, Sérgio Lima, Martyn Pillinger, and Anabela
A. Valente
8.1 Carbohydrates for Life ................................ 167
8.2 Furfural-Evolution over Nearly Two Centuries .......... 169
8.3 Applications of Furfural .............................. 169
8.4 Mechanistic Considerations on the Conversion of
Pentosans into Furfural ............................... 170
8.5 Production of Furfural ................................ 172
8.5.1 Crystalline Microporous Silicates .............. 173
8.5.2 Functionalized Mesoporous Silicas .............. 274
8.5.3 Transition Metal Oxide Nanosheets .............. 179
8.6 Conclusion and Future Perspectives .................... 180
Acknowledgments ....................................... 182
References ............................................ 182
9 Multiple Bond-Forming Transformations: the Key Concept
Toward Eco-Compatible Synthetic Organic Chemistry .......... 187
Yoann Coquerel, Thomas Boddaert, Marc Presset, Damien
Mailhol, and Jean Rodriguez
9.1 The Science of Synthesis .............................. 187
9.2 Multiple Bond-Forming Transformations (MBFTs) ......... 190
9.2.1 Consecutive Reactions .......................... 190
9.2.2 Domino Reactions ............................... 190
9.2.3 Multicomponent Reactions ....................... 191
9.2.4 One-Pot Reactions .............................. 191
9.3 An Account of Our Recent Contributions ................ 192
9.3.1 MВFTs Involving a Wolff Rearrangement .......... 192
9.3.2 MB FTs Involving Metals ........................ 194
9.3.3 MBFTs Involving Anions ......................... 196
9.4 Conclusion ............................................ 200
References ............................................ 200
10 Modeling of Indirect Phototransformation Reactions in
Surface Waters ............................................. 203
Davide Vione, Radharani Das, Francesca Rubertelli, Valte
Maurino, and Claudio Minero
10.1 Introduction .......................................... 203
10.2 Indirect Photolysis Processes in Surface Waters ....... 205
10.2.1 Reactions Induced by •OH ....................... 206
10.2.2 Reactions Induced by СО3-• ...................... 209
10.2.3 Reactions Induced by 3CDOM* ..................... 211
10.2.4 Other Reactions ................................ 212
10.3 Modeling the Photochemistry of Surface Waters ......... 214
10.3.1 Modeling the Absorption Spectrum of Lake
Water .......................................... 214
10.3.2 Mass versus Concentration Approach in
Photochemistry Models .......................... 216
10.3.3 Radiation Absorption by Photoactive Water
Components ..................................... 217
10.3.4 Generation and Reactivity of •OH upon
Irradiation of CDOM, Nitrate, and Nitrite ...... 218
10.3.5 Formation and Reactivity of СО3-• in Surface
Waters ......................................... 223
10.3.5.1 Oxidation of HСО3-• and СО32- by •OH ... 224
10.3.5.2 Oxidation of СО32- by 3CDOM* ........... 224
10.3.5.3 Reactivity of СО3-• in Surface
Waters ................................ 225
10.3.6 Formation and Reactivity of 3CDOM* in Surface
Waters ......................................... 226
10.4 Conclusions and Perspectives .......................... 230
Acknowledgment ........................................ 231
References ............................................ 231
Part IV Organic Synthesis and Materials ...................... 235
11 Bottom-Up Approaches to Nanographenes through Organic
Synthesis .................................................. 237
Diego Реñа
11.1 I ntr oduction ........................................ 237
11.2 Alternant Polyarenes with 10 Fused Benzene Rings ...... 239
11.3 Alternant Polyarenes with 11 Fused Benzene Rings ...... 244
11.4 Alternant Polyarenes with 12 Fused Benzene Rings ...... 248
11.5 Alternant Polyarenes with 13 Fused Benzene Rings ...... 249
11.6 Alternant Polyarenes with 14 Fused Benzene Rings ...... 252
11.7 Alternant Polyarenes with More than 15 Fused Benzene
Rings ................................................. 252
11.8 Conclusions and Outlook ............................... 256
Acknowledgments ............................................ 257
References ................................................. 257
12 Differentiated Ligands for the Sequential Construction
of Crystalline HeterometaUic Assemblies .................... 263
Stéphane A. Baudron
12.1 Introduction .......................................... 263
12.2 Dithiolate Ligands .................................... 268
12.2.1 Metallatectons ................................. 268
12.2.2 Infinite Chains ................................ 270
12.2.3 Discrete Assemblies ............................ 271
12.3 Dipyrrin Ligands ...................................... 273
12.3.1 Metallatectons ................................. 274
12.3.2 HeterometaUic Architectures Built with the
Assistance of an Ag-π Interaction .............. 274
12.4 Conclusion and Outlook ................................ 277
Acknowledgments ....................................... 278
References ............................................ 278
13 Water-Soluble Perylene Dyes ................................ 283
Cordula D. Schmidt and Andreas Hirsch
13.1 History and Functionalization of Perylene Dyes ........ 283
13.2 Derivatization of Perylene Dyes ....................... 284
13.3 Properties and Applications of Perylene Dyes .......... 286
13.4 Advantages and Applications of Water-Soluble
Perylene Derivatives .................................. 286
13.5 Symmetric Water-Soluble PDIs .......................... 289
13.6 Unsymmetric PDIs ...................................... 292
13.6.1 Noncovalent Functionalization of Carbon
Nanotubes ...................................... 293
13.6.2 PDIs as Reporter Electrolytes for
Implantation Technology ........................ 296
13.7 Chiral Water-Soluble PDIs ............................. 297
13.8 Conclusion and Outlook ................................ 300
Acknowledgments ....................................... 301
References ............................................ 301
Index ......................................................... 305
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