Reflecting the tremendous growth of this hot topic in recent years, this book covers C-H activation with a focus on heterocycle synthesis.
As such, the text provides general mechanistic aspects and gives a comprehensive overview of catalytic reactions in the presence of palladium, rhodium, ruthenium, copper, iron, cobalt, and iridium. The chapters are organized according to the transition metal used and sub-divided by type of heterocycle formed to enable quick access to the synthetic route needed. Chapters on carbonylative synthesis of heterocycles and the application of C-H activation methodology to the synthesis of natural products are also included.
Written by an outstanding team of authors, this is a valuable reference for researchers in academia and industry working in the field of organic synthesis, catalysis, natural product synthesis, pharmaceutical chemistry, and crop protection.
Autorentext
Inhalt
List of Contributors XXI
Foreword 1 XXVII
Foreword 2 XXIX
Preface XXXI
1 Computational Studies of Heteroatom-Assisted CH Activation at Ru, Rh, Ir, and Pd as a Basis for Heterocycle Synthesis and Derivatization 1
Kevin J. T. Carr, Stuart A. Macgregor, and Claire L. McMullin
1.1 Introduction 1
1.2 Palladium 2
1.2.1 Intramolecular Heteroatom-Assisted CH Activation 2
1.2.1.1 Early Computational Studies 2
1.2.1.2 The Role of the Base, Solvent, and Additives on Pd-Mediated Intramolecular CH Activation 5
1.2.1.3 Intramolecular CH Activation of Heterocyclic Substrates 9
1.2.2 Intermolecular CH Activation 11
1.2.2.1 Early Computational Studies 11
1.2.2.2 Direct Functionalization via CH Activation of Heterocyclic Substrates 15
1.3 Ruthenium, Rhodium, and Iridium 22
1.3.1 Intramolecular Heteroatom-Assisted CH Activation 22
1.3.2 Intermolecular CH Activation 25
1.3.3 CH Activation and Functionalization 27
1.3.3.1 Heterocycle Formation with Internal Oxidants 28
1.3.3.2 Heterocycle Formation without Internal Oxidants 34
1.3.4 Alkenylation and Amination 38
1.4 Conclusions 40
Acknowledgments 41
References 41
2 Pd-Catalyzed Synthesis of Nitrogen-Containing Heterocycles 45
Lixin Li, Xiaolei Ji, and Hanming Huang
2.1 Introduction 45
2.2 General Consideration on Palladium Chemistry 45
2.3 Heterocycle Synthesis via C(sp3)H Activation 46
2.3.1 Heterocycle Synthesis via Activated C(sp3)H Bonds 47
2.3.2 Heterocycle Synthesis via Unactivated C(sp3)H Bonds 49
2.4 Heterocycles via C(sp2)H Activation 55
2.5 Conclusions 61
References 62
3 Pd-Catalyzed Synthesis of Oxygen-Containing Heterocycles 65
Yudong Yang and Jingsong You
3.1 Introduction 65
3.2 Palladium-Catalyzed CH Activation/CC Formation to Construct Oxacycles 66
3.2.1 Palladium-Catalyzed CH Bond Arylation 67
3.2.2 Palladium-Catalyzed CH Olefination 69
3.2.3 Palladium-Catalyzed CH Alkylation 75
3.2.4 Palladium-Catalyzed CH Carbonylation and Carboxylation 76
3.3 Palladium-Catalyzed CH Activation/CO Formation to Construct Oxacycles 80
3.3.1 Palladium-Catalyzed CO Bond Formation via C(sp2)H Activation 81
3.3.2 Palladium-Catalyzed CO Bond Formation via Allylic CH Activation 84
3.4 Conclusions 86
References 87
4 Pd-Catalyzed Synthesis of Other Heteroatom-Containing Heterocycles 91
Zhanxiang Liu and Yuhong Zhang
4.1 Introduction 91
4.2 Sulfur-Containing Heterocycles 91
4.2.1 Benzo[b]thiophenes 92
4.2.2 Benzothiazoles 95
4.2.3 Sultones 98
4.2.4 Sultams 100
4.3 Phosphorus-Containing Heterocycles 102
4.3.1 PC Heterocycles (Dibenzophosphole Oxides) 102
4.3.2 OP=OHeterocycles 106
4.3.3 PN Heterocycles 107
4.4 Silicon-Containing Heterocycles 108
4.4.1 Benzosiloles 108
4.4.2 Oxasiline and Azasiline 110
4.5 Summary and Conclusions 112
References 113
5 Rh-Catalyzed Synthesis of Nitrogen-Containing Heterocycles 117
Krishnamoorthy Muralirajan and Chien-Hong Cheng
5.1 Introduction 117
5.2 Synthesis of Five-Membered Nitrogen Heterocycles 118
5.2.1 Synthesis of Indoles 118
5.2.2 Synthesis of Isoindolines 122
5.2.3 Synthesis of Unprotected Indoles 123
5.2.4 Synthesis of Indolines 124
5.2.5 Synthesis of Indazoles 124
5.2.6 Synthesis of Isoxazoles 125
5.2.7 Synthesis of Pyrroles 126
5.2.8 Synthesis of Isoindolin-1-ones 128
5.2.9 Synthesis of 3-Hydroxyisoindolin-1-ones 129
5.2.10 Synthesis of 3-(Imino)isoindolinones 129
5.2.11 Synthesis of Dih...