Visible Light Photocatalysis in Organic Chemistry

Filling the need for a ready reference that reflects the vast developments in this field, this book presents everything from fundamentals, applications, various reaction types, and technical applications. Edited by rising stars in the scientific community, the text focuses solely on visible light photocatalysis in the context of organic chemistry. This primarily entails photo–induced electron transfer and energy transfer chemistry sensitized by polypyridyl complexes, yet also includes the use of organic dyes and heterogeneous catalysts. A valuable resource to the synthetic organic community, polymer and medicinal chemists, as well as industry professionals. INDICE: 1 An Overview of the Physical and Photophysical Properties of [Ru(bpy)3]2+ 1DanielaM. Arias–Rotondo and James K. McCusker .1.1 Introduction 1 .1.2 [Ru(bpy)3]2+: Optical and Electrochemical Properties 4 .1.2.1 Optical Properties 4 .1.2.2 Electrochemical Properties 6 .1.3 Excited State Kinetics 8 .1.3.1 Steady–State Emission 8 .1.3.2 Time–Resolved Emission 10 .1.4 Excited–State Reactivity of [Ru(bpy)3]2+ 11 .1.5 Energy Transfer: Förster and Dexter Mechanisms 12 .1.6 Electron Transfer 14 .1.7 Probing the Mechanism, Stage I: Stern Volmer Quenching Studies 14 .1.8 Probing the Mechanism, Stage II: Electron Versus Energy Transfer 16 .1.9 Designing Photocatalysts: [Ru(bpy)3]2+ as a Starting Point 20 .1.10 Conclusion 22 .References 23 .2 Visible–Light–Mediated Free Radical Synthesis 25Louis Fensterbank, Jean–Philippe Goddard, and Cyril Ollivier .2.1 Introduction 25 .2.2 Basics of the Photocatalytic Cycle 26 .2.3 Generation of Radicals 27 .2.3.1 Formation of C–Centered Radicals 27 .2.3.1.1 Dehalogenation (I, Br, Cl) 27 .2.3.1.2 Other C–Heteroatom Cleavage 29 .2.3.1.3 C C Bond Cleavage 29 .2.3.2 Formation of N–Centered Radicals 30 .2.4 C X Bond Formation 30 .2.4.1 C O Bond 30 .2.4.2 C N Bond 32 .2.4.3 C S and C Se Bonds 33 .2.4.4 C Br Bond 34 .2.4.5 C F Bond 34 .2.4.6 C B Bond 35 .2.5 C C Bond Formation 35 .2.5.1 Formation and Reactivity of Aryl Radicals 35 .2.5.2 Formation and Reactivity of Trifluoromethyl and Related Radicals 40 .2.5.2.1 Photocatalyzed Reduction of Perfluorohalogen Derivatives 40 .2.5.2.2 Photocatalyzed Reduction of Perfluoroalkyl–Substituted Onium Salts 42 .2.5.2.3 Photocatalyzed Formation of Perfluoroalkyl Radicals from Sulfonyl and Sulfinyl Derivatives 43 .2.5.3 Formation and Reactivity of Alkyl and Related Radicals 45 .2.5.3.1 C C Bond FormationThrough Photocatalyzed Reduction of Halogen Derivatives and Analogs 45 .2.5.3.2 C C Bond FormationThrough Photocatalyzed Oxidation of Electron–Rich Functional Group 47 .2.5.3.3 C C Bond FormationThrough Photocatalyzed Oxidation of Amino Group 48 .2.6 Radical Cascade Applications 49 .2.6.1 Intramolecular Polycyclization Processes 49 .2.6.2 Sequential Inter– and Intramolecular Processes 51 .2.6.3 Sequential Radical and Polar Processes 56 .References 59 .3 AtomTransfer Radical Addition using Photoredox Catalysis 73Theresa M.Williams and Corey R. J. Stephenson .3.1 Introduction 73 .3.2 Transition Metal–Catalyzed ATRA 77 .3.2.1 Ruthenium– and Iridium–Based ATRA 77 .3.2.1.1 Mechanistic Investigations 77 .3.2.1.2 Ruthenium– and Iridium–Based ATRA 80 .3.2.2 Copper–Mediated ATRA 81 .3.2.2.1 Trifluoromethylation 82 .3.3 Other Photocatalysts for ATRA Transformations 84 .3.3.1 p–Anisaldehyde 84 .3.4 Semiconductor 86 .3.5 Atom Transfer Radical Cyclization (ATRC) 87 .3.6 Atom Transfer Radical Polymerization (ATRP) 89 .3.7 Conclusion 90 .References 90 .4 Visible Light Mediated –Amino C H Functionalization Reactions 93You–Quan Zou andWen–Jing Xiao .4.1 Introduction 93 .4.2 Visible Light Mediated –Amino C H Functionalization Via Iminium Ions 95 .4.2.1 Aza–Henry Reaction 95 .4.2.2 Mannich Reaction 100 .4.2.3 Strecker Reaction 104 .4.2.4 Friedel Crafts Reaction 105 .4.2.5 Alkynylation Reaction 108 .4.2.6 Phosphonation Reaction 109 .4.2.7 Addition of 1,3–Dicarbonyls 109 .4.2.8 Formation of C N and C O Bonds 110 .4.2.9 Miscellaneous 112 .4.3 Visible Light Mediated –Amino C H Functionalization Via –Amino Radicals 116 .4.3.1 Addition to Electron–Deficient Aromatics 116 .4.3.2 Addition to Electron–Deficient Alkenes 116 .4.3.3 Miscellaneous 120 .4.4 Conclusions and Perspectives 121 .References 122 .5 Visible Light Mediated Cycloaddition Reactions 129Scott Morris, Theresa Nguyen, and Nan Zheng .5.1 Introduction 129 .5.2 [2+2] Cycloadditions: Formation of Four–Membered Rings 130 .5.2.1 Introduction to [2+2] Cycloadditions 130 .5.2.2 Utilization of the Reductive Quenching Cycle 130 .5.2.3 Utilization of the Oxidative Quenching Cycle 135 .5.2.4 Utilization of Energy Transfer 139 .5.2.5 [2+2] Conclusion 142 .5.3 [3+2] Cycloadditions: Formation of Five–Membered Rings 143 .5.3.1 Introduction to [3+2] Cycloadditions 143 .5.3.2 [3+2] Cycloaddition of Cyclopropylamines 143 .5.3.3 1,3–Dipolar Cycloaddition of Azomethine Ylides 145 .5.3.4 [3+2] Cycloaddition of Aryl Cyclopropyl Ketones 146 .5.3.5 [3+2] Cycloaddition via ATRA/ATRC 146 .5.3.6 [3+2] Conclusion 148 .5.4 [4+2] Cycloadditions: Formation of Six–Membered Rings 149 .5.4.1 Introduction to [4+2] Cycloadditions 149 .5.4.2 [4+2] Cycloadditions Using Radical Anions 149 .5.4.3 [4+2] Cycloadditions Using Radical Cations 151 .5.4.4 [4+2] Conclusion 154 .5.5 Conclusion 155 .References 156 .6 Metal–Free Photo(redox) Catalysis 159Kirsten Zeitler .6.1 Introduction 159 .6.1.1 Background 162 .6.1.2 Classes of Organic Photocatalysts 162 .6.2 Applications of Organic Photocatalysts 166 .6.2.1 Energy Transfer Reactions 166 .6.2.2 Reductive Quenching of the Catalyst 171 .6.2.2.1 Cyanoarenes 171 .6.2.2.2 Quinones 172 .6.2.2.3 Cationic Dyes: Pyrylium, Quinolinium, and Acridinium Scaffolds 173 .6.2.2.4 Xanthene Dyes and Further Aromatic Scaffolds 188 .6.2.3 Oxidative Quenching of the Catalyst 203 .6.2.4 New Developments 214 .6.2.4.1 Upconversion 215 .6.2.4.2 Consecutive Photoelectron Transfer 215 .6.2.4.3 Multicatalysis 216 .6.3 Conclusion and Outlook 224 .References 224 .7 Visible Light and Copper Complexes: A Promising Match in Photoredox Catalysis 233Suva Paria and Oliver Reiser .7.1 Introduction 233 .7.2 Photophysical Properties of Copper Catalysts 234 .7.3 Application of Copper Based Photocatalysts in Organic Synthesis 237 .7.4 Outlook 247 .Acknowledgment 248 .References 248 .8 Arene Functionalization by Visible Light Photoredox Catalysis 253Durga Hari Prasad, Thea Hering, and Burkhard König .8.1 Introduction 253 .8.1.1 Aryl Diazonium Salts 253 .8.1.2 Diaryl Iodonium Salts 268 .8.1.3 Triaryl Sulfonium Salts 272 .8.1.4 Aryl Sulfonyl Chlorides 273 .8.2 Applications of Aryl Diazonium Salts 274 .8.3 Photoinduced Ullmann C N Coupling 276 .8.4 Conclusion 278 .References 278 .9 Visible–Light Photocatalysis in the Synthesis of Natural Products 283Gregory L. Lackner, KyleW. Quasdorf, and Larry E. Overman .References 295 .10 Dual Photoredox Catalysis: TheMerger of Photoredox Catalysis with Other Catalytic Activation Modes 299Christopher K. Prier and DavidW. C. MacMillan .10.1 Introduction 299 .10.2 Merger of Photoredox Catalysis with Organocatalysis 300 .10.3 Merger of Photoredox Catalysis with Acid Catalysis 314 .10.3.1 Photoredox Catalysis and Brønsted Acid Catalysis 314 .10.3.2 Photoredox Catalysis and Lewis Acid Catalysis 318 .10.4 Merger of Photoredox Catalysis with Transition Metal Catalysis 320 .10.5 Conclusions 328 .References 328 .11 Enantioselective Photocatalysis 335Susannah C. Coote and Thorsten Bach .11.1 Introduction 335 .11.2 The Twentieth Century: PioneeringWork 336 .11.3 The Twenty–First Century: Contemporary Developments 341 .11.3.1 Large–Molecule Chiral Hosts 341 .11.3.2 Small–Molecule Chiral Photosensitizers 343 .11.3.3 Lewis Acid–Mediated Photoreactions 353 .11.4 Conclusions and Outlook 357 .References 358 .12 Photomediated Controlled Polymerizations 363Nicolas J. Treat, Brett P. Fors, and Craig J. Hawker .12.1 Catalyst Activation by Light 365 .12.1.1 Cu–Catalyzed Photoregulated Atom Transfer Radical Polymerizations (photoATRP) 365 .12.1.2 Photomediated ATRP with Non–Copper–Based Catalyst Systems 368 .12.1.3 Iodine–Mediated Photopolymerizations 371 .12.1.4 Metal–Free Photomediated Ring–Opening Metathesis Polymerization 375 .12.1.5 Photoregulated Reversible–Addition Fragmentation Chain Transfer Polymerizations (photoRAFT) 376 .12.2 Chain–End Activation by Light 383 .12.3 Conclusions 384 .References 385 .13 Accelerating Visible–Light Photoredox Catalysis in Continuous–Flow Reactors 389Natan J.W. Straathof and Timothy Noël .13.1 Introduction 389 .13.2 Homogeneous Photocatalysis in Single–Phase Flow 392 .13.3 Gas liquid Photocatalysis in Flow 401 .13.4 Heterogeneous Photocatalysis in Flow 408 .13.5 Conclusions 410 .Conflict of Interest 410 .References 410 .14 The Application of Visible–Light–Mediated Reactions to the Synthesis of Pharmaceutical Compounds 415James. J. Douglas .14.1 Introduction 415 .14.2 Asymmetric Benzylation 415 .14.3 Amide Bond Formation 416 .14.4 C H Azidation 417 .14.5 Visible–Light–Mediated Benzothiophene Synthesis 418 .14.6 –Amino Radical Functionalization 419 .14.7 Visible–Light–Mediated Radical Smiles Rearrangement 422 .14.8 Photoredox and Nickel Dual Catalysis 423 .14.9 The Scale–Up of Visible–Light–Mediated Reactions Via Continuous .Processing 426 .References 428 .Index 431

• ISBN: 978-3-527-33560-2
• Editorial: Wiley VCH
• Encuadernacion: Cartoné
• Páginas: 456
• Fecha Publicación: 14/03/2018
• Nº Volúmenes: 1
• Idioma: Inglés