List of Contributors XXIII
Introduction XXXV
1 Diversity-Oriented Syntheses of Natural Products and Natural Product-Like Compounds 1
Ling-Min Xu, Yu-Fan Liang, Qin-Da Ye, and Zhen Yang
1.1 Introduction 1
1.2 Diversity-Oriented Synthesis (DOS) 2
1.3 Diverted Total Synthesis (DTS) 7
1.4 Function-Oriented Synthesis (FOS) 9
1.5 Target-Oriented Synthesis (TOS) 11
1.6 Conclusion and Perspectives 24
Acknowledgments 26
References 26
Commentary Part 28
Comment 1 28
Michael Foley
Comment 2 29
Scott A. Snyder
Comment 3 30
Da-Wei Ma
Authors’ Response to the Commentaries 31
References 31
2 Total Synthesis of Natural Products and the Synergy with Synthetic Methodology 33
Qian Wang and Jie-Ping Zhu
2.1 Introduction 33
2.2 Domino Process 36
2.3 Multicomponent Reactions 43
2.4 Oxidative Anion Coupling 52
2.5 Pattern Recognition 60
2.6 Conformation-Directed Cyclization 65
2.7 Conclusion and Perspectives 69
Acknowledgments 70
References 70
Commentary Part 72
Comment 1 72
Kyriacos C. Nicolaou
Comment 2 73
Henry N.C. Wong
Comment 3 75
Wei-Dong Li
References 77
3 Interplay Between the Chemical Space and the Biological Space 81
Ren-Xiao Wang
3.1 Chemical Biology: Historical and Philosophical Aspects 81
3.2 Preparation of Chemical Libraries 90
3.3 Screening Strategies 95
3.4 Target Elucidation and Validation 106
3.5 Conclusion and Perspectives 116
References 117
Commentary Part 121
Comment 1 121
Ke Ding
Comment 2 121
Li-He Zhang
Comment 3 122
Jun-Ying Yuan
Author’s Response to the Commentaries 122
References 123
4 Biosynthesis of Pharmaceutical Natural Products and Their Pathway Engineering 125
Michael J. Smanski, Xu-Dong Qu, Wen Liu, and Ben Shen
4.1 Introduction 125
4.2 Expanded Paradigms in Biosynthetic Logic 126
4.3 New Approaches to NP Biosynthesis Research 147
4.4 Better Understanding of the Scope and Diversity of NP Production 156
4.5 Future Perspectives 168
Acknowledgments 170
Abbreviations 171
References 171
Commentary Part 178
Comment 1 178
Yi Tang
Comment 2 178
Yi Yu and Zi-Xin Deng
Authors’ Response to the Commentaries 179
Response to Yi Tang 179
Response to Yi Yu and Zixin Deng 179
5 Carbohydrate Synthesis Towards Glycobiology 181
Biao Yu and Lai-Xi Wang
5.1 Introduction 181
5.2 Advances in Chemical Glycosylation 182
5.3 New Strategies in Oligosaccharide Assembly 189
5.4 Enzymatic and Chemoenzymatic Methods 193
5.5 Synthesis of Heparin and Heparan Sulfate Oligosaccharides 195
5.6 Synthesis of Homogeneous Glycoproteins 200
5.7 Synthesis of Carbohydrate-Containing Complex Natural Compounds 206
5.8 Conclusion and Perspectives 212
Acknowledgments 212
References 212
Commentary Part 218
Comment 1 218
Sam Danishefsky
Comment 2 218
David Crich
Authors’ Response to the Commentaries 219
References 219
6 Chemical Synthesis of Proteins 221
Lei Liu
6.1 Introduction 221
6.2 Brief History 222
6.3 Current Technology 227
6.4 Applications 236
6.5 Conclusion and Perspectives 242
References 242
Commentary Part 244
Comment 1 244
Sam Danishefsky
Comment 2 244
David Crich
References 245
7 CuAAC: the Quintessential Click Reaction 247
Valery V. Fokin
7.1 Introduction 247
7.2 Azide–Alkyne Cycloaddition: the Basics 249
7.3 CuAAC: Catalysts and Ligands 251
7.4 Mechanistic Aspects of the CuAAC 258
7.5 Reactions of 1-Iodoalkynes 264
7.6 Examples of Application of the CuAAC Reaction 266
7.7 Reactions of Sulfonyl Azides 269
7.8 Outlook/Perspective 273
Acknowledgments 273
References 273
Commentary Part 276
Comment 1 276
Krzysztof Matyjaszewski
References 276
8 Transition Metal-Catalyzed C–H Functionalization: Synthetically Enabling Reactions for Building Molecular Complexity 279
Keary M. Engle and Jin-Quan Yu
8.1 Introduction 279
8.2 Background and Early Work 281
8.3 First Functionalization: Challenges in Hydrocarbon Chemistry 293
8.4 Further Functionalization: C–H Bonds as Reaction Partners in Organic Synthesis 300
8.5 Catalytic C–H Functionalization via Metal Insertion 303
8.6 Other Emerging Metal-Catalyzed Further Functionalization Methods 311
8.7 Outlook and Conclusion 321
Acknowledgments 322
Abbreviations 322
References 323
Commentary Part 328
Comment 1 328
Huw M.L. Davies
Comment 2 329
Zhenfeng Xi
Comment 3 330
Shu-Li You
Comment 4 332
Zhang-Jie Shi
Authors’ Response to the Commentaries 333
References 333
9 An Overview of Recent Developments in Metal-Catalyzed Asymmetric Transformations 335
Christian A. Sandoval and Ryoji Noyori
9.1 Introduction 335
9.2 Asymmetric Carbon–Carbon Bond Formation 336
9.3 Asymmetric Reductions and Oxidations 348
9.4 Conclusion 353
References 353
Commentary Part 363
Comment 1 363
Qi-Lin Zhou
Comment 2 363
Andreas Pfaltz
Comment 3 365
Xue-Long Hou
Comment 4 365
Hisashi Yamamoto
References 366
10 The Proline-Catalyzed Mannich Reaction and the Advent of Enamine Catalysis 367
Benjamin List and Sai-Hu Liao
10.1 Introduction 367
10.2 The Proline-Catalyzed Mannich Reaction 367
10.3 Conclusion 374
References 374
Commentary Part 375
Comment 1 375
Seiji Shirakawa and Keiji Maruoka
Comment 2 377
The Early Status of Asymmetric Organocatalysis 377
Liu-Zhu Gong
Milestone in Asymmetric Organocatalysis 378
Enamine Catalysis 378
Iminium Catalysis 378
Domino Reactions by Amine Catalysis 378
Hydrogen Bonding Catalysis 378
Conclusion 379
Comment 3 379
Wen-Jing Xiao
References 382
11 Recent Topics in Cooperative Catalysis: Asymmetric Catalysis, Polymerization, Hydrogen Activation, and Water Splitting 385
Motomu Kanai
11.1 Introduction 385
11.2 Cooperative Catalysis in Asymmetric Reactions 387
11.3 Cooperative Catalysis in Alkene Polymerization 393
11.4 Cooperative Catalysis in Hydrogen Activation/Generation 394
11.5 Conclusion and Perspectives 398
References 398
Commentary Part 401
Comment 1 401
Takao Ikariya
Comment 2 402
Takashi Ooi
Comment 3 405
Kuiling Ding
Comment 4 409
David Milstein
Authors’ Response to the Commentaries 410
References 411
12 Flourishing Frontiers in Organofluorine Chemistry 413
G. K. Surya Prakash and Fang Wang
12.1 Introduction 413
12.2 Synthetic Approaches for the Introduction of Fluorine-Containing Functionalities and Related Chemistry 415
12.3 Conclusion and Perspectives 459
Acknowledgment 460
References 460
Commentary Part 470
Comment 1 470
David O’Hagan
Comment 2 471
Jinbo Hu
Comment 3 472
Kuiling Ding and Li-Xin Dai
Authors’ Response to the Commentaries 472
References 473
Addendum 473
13 Supramolecular Organic Chemistry: the Foldamer Approach 477
Zhan-Ting Li
13.1 Introduction 477
13.2 Foldamers: the Background 479
13.3 Molecular Recognition 480
13.4 Homoduplex 497
13.5 Organogels 499
13.6 Vesicles 501
13.7 Supramolecular Liquid Crystals 502
13.8 Macrocycles 503
13.9 Catalysis 510
13.10 Macromolecular Self-Assembly 514
13.11 Conclusion and Perspectives 516
Acknowledgments 517
References 517
Commentary Part 520
Comment 1 520
Peter J. Stang
Comment 2 521
Liang Zhao and Mei-Xiang Wang
Introduction 521
Macrocyclic Compounds 522
Cycloparaphenylenes 522
Pillar[n]arenes 524
Heteracalixaromatics 525
Noncovalent Interactions 527
Quadruple Hydrogen Bonding 527
Halogen Bonding 528
Anion–π Interaction 529
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