Оглавление
Группа авторов. Remote C-H Bond Functionalizations
Table of Contents
List of Tables
List of Illustrations
Guide
Pages
Remote CH Bond Functionalizations. Methods and Strategies in Organic Synthesis
1 Introduction
2 Transition Metal‐Catalyzed Remote meta‐C–H Functionalization of Arenes Assisted by meta‐Directing Templates
2.1 Introduction
2.2 Template‐Assisted meta‐C–H Functionalization. 2.2.1 Toluene Derivatives
2.2.2 Acid Derivatives. 2.2.2.1 Hydrocinnamic Acid Derivatives
2.2.2.2 Phenylacetic Acid Derivatives
2.2.2.3 Benzoic Acid Derivatives
2.2.3 Amine and N‐Heterocyclic Arene Derivatives. 2.2.3.1 Aniline Derivatives
2.2.3.2 Benzylamine Derivatives
2.2.3.3 Phenylethylamine Derivatives
2.2.3.4 N‐Heterocyclic Arene Derivatives
2.2.4 Sulfonic Acid Derivatives
2.2.5 Phenol Derivatives
2.2.6 Alcohol Derivatives
2.2.7 Silane Derivatives
2.2.8 Phosphonate Derivatives
2.3 Mechanistic Considerations
2.4 Conclusion
Abbreviations
References
3 C–H Functionalization of Arenes Under Palladium/Norbornene Catalysis
3.1 Introduction
3.2 Pd(0)‐Catalyzed C–H Functionalization of Aryl (Pseudo)Halides
3.2.1 ortho‐Alkylation. 3.2.1.1 ortho‐Alkylation with Simple Alkyl Halides
3.2.1.2 ortho‐Alkylation with Bifunctional Alkylating Reagents
3.2.1.3 ortho‐Alkylation with Three‐Membered Heterocycles
3.2.2 ortho‐Arylation
3.2.3 ortho‐Acylation and Alkoxycarbonylation
3.2.4 ortho‐Amination
3.2.5 ortho‐Thiolation
3.3 Pd(II)‐Catalyzed C–H Functionalization of Arenes
3.3.1 C2‐Functionalization of Indoles and Pyrroles
3.3.2 meta‐C–H Functionalization of Arenes Containing an ortho‐Directing Group
3.3.3 ortho‐C–H Functionalization of Arylboron Species
3.4 Conclusions and Outlook
Acknowledgments
References
4 Directing Group Assisted meta‐C–H Functionalization of Arenes Aided by Norbornene as Transient Mediator
4.1 Introduction
4.2 meta‐C–H Alkylation of Arenes. 4.2.1 Amide as Directing Group
4.2.2 Sulfonamide as Directing Group
4.3 meta‐C–H Arylation of Arenes. 4.3.1 Amide as Directing Group
4.3.2 Sulfonamide as Directing Group
4.3.3 Tertiary Amine as Directing Group
4.3.4 Tethered Pyridine‐Type Directing Group
4.3.5 Acetal‐Based Quinoline as Directing Group
4.3.6 Free Carboxylic Acid as Directing Group
4.4 meta‐C–H Chlorination of Arenes
4.5 meta‐C–H Amination of Arenes
4.6 meta‐C–H Alkynylation of Arenes
4.7 Enantioselective meta‐C–H Functionalization
4.8 Conclusion
Abbreviations
References
5 Ruthenium‐Catalyzed Remote C–H Functionalizations
5.1 Introduction
5.2 meta‐C–H Functionalizations. 5.2.1 C–H Alkylation
5.2.2 C–H Benzylation
5.2.3 C–H Carboxylation
5.2.4 C–H Acylation
5.2.5 C–H Sulfonylation
5.2.6 C–H Halogenation
5.2.7 C–H Nitration
5.3 para‐C–H Functionalizations
5.4 meta‐/ortho‐C–H Difunctionalizations
5.5 Conclusions
Acknowledgments
References
6 Harnessing Non‐covalent Interactions for Distal C(sp2)–H Functionalization of Arenes
6.1 Introduction
6.2 Non‐covalent Interactions in Metal Catalyzed CH Bond Functionalization
6.3 Overview of Iridium‐Catalyzed Borylation
6.4 Non‐covalent Interactions in Ir‐Catalyzed Borylation
6.5 meta‐Selective Borylation using Non‐covalent Interactions
6.6 para‐Selective Borylation using Non‐covalent Interactions
6.7 Conclusions
References
7 The Non‐directed Distal C(sp2)–H Functionalization of Arenes
7.1 Introduction
7.1.1 Mechanisms
7.2 C–Het Formation
7.2.1 Borylation
7.2.2 Silylation
7.2.3 Amination
7.2.4 Oxygenation
7.2.5 Other CHet Bond Forming Reactions
7.3 CC Bond Forming Reactions
7.3.1 C–H‐Arylation
7.3.2 Alkenylation/Olefination
7.3.3 Cyanation
7.3.4 Other CC Bond Forming Reactions
7.4 Outlook
References
Note
8 Transition Metal Catalyzed Distal para‐Selective C–H Functionalization
8.1 Introduction
8.2 Template Assisted para‐Selective C–H Functionalization
8.2.1 Palladium Catalyzed Methods. 8.2.1.1 Alkenylation
8.2.1.2 Silylation
8.2.1.3 Ketonization
8.2.1.4 Acetoxylation
8.2.1.5 Cyanation
8.2.2 Rhodium Catalyzed Functionalization. 8.2.2.1 Alkenylation
8.3 Steric Controlled and Lewis Acid‐Transition Metal Cooperative Catalysis
8.3.1 Nickel Catalyzed Methods. 8.3.1.1 Alkylation and Alkenylation
8.3.2 Iridium Catalyzed Methods. 8.3.2.1 Borylation
8.4 Non‐covalent Interaction Induced para‐C–H Functionalization. 8.4.1 Di‐polar Induced Methods
8.4.2 Ion‐Pair Induced Methods
8.5 Conclusion and the Prospect
Acknowledgments
References
9 Regioselective C–H Functionalization of Heteroaromatics at Unusual Positions
9.1 Introduction
9.2 Indole
9.2.1 C–H Functionalization at C4 Position
9.2.2 C–H Functionalization at C7 Position
9.2.3 C–H Functionalization at C5 Position
9.2.4 C–H Functionalization at C6 Position
9.3 (Benzo)Thiophene
9.4 Pyrrole
9.5 Pyridine
9.6 Miscellaneous Heteroarenes. 9.6.1 Thiazole
9.6.2 Quinoline
9.7 Conclusion
References
10 Directing Group Assisted Distal C(sp3)–H Functionalization of Aliphatic Substrates
10.1 Introduction
10.2 γ‐C(sp3)–H Functionalization of Aliphatic Acids
10.3 δ‐/ɛ‐C(sp3)H Bond Functionalization of Aliphatic Amines
10.4 γ‐C(sp3)H Bond Functionalization of Aliphatic Ketones or Aldehydes
10.5 γ‐/δ‐C(sp3)H Bond Functionalization of Aliphatic Alcohols
10.6 Conclusions and Outlook
References
11 Radically Initiated Distal C(sp3)–H Functionalization
11.1 Introduction
11.2 Distal C(sp3)–H Functionalization Promoted by Carbon‐Centered Radicals
11.3 Distal C(sp3)–H Functionalization Promoted by Nitrogen‐Centered Radicals
11.3.1 Generation of Nitrogen Radical from NX (X = F, Cl, Br, I) Bond
11.3.2 Generation of Nitrogen Radical from NN Bond
11.3.3 Generation of Nitrogen Radical from NO Bond
11.3.4 Nitrogen Radical Generated Directly from NH Bond
11.4 Oxygen‐Centered Radicals Initiate Distal C(sp3)–H Functionalization
11.4.1 Oxygen Radical Generated from OX (X = N, O) bond
11.4.2 Oxygen Radical Generated Directly from OH Bond
11.5 Summary and Outlook
References
12 Non‐Directed Functionalization of Distal C(sp3)H Bonds
12.1 Introduction
12.1.1 Bond Dissociation Energy (BDE) of CH Bonds
12.1.2 Scope of the Chapter
12.2 Reactions Occurring Without Formation of Metal–Carbon Bonds. 12.2.1 Oxidations with Dioxiranes
12.2.2 Decatungstate‐Photocatalyzed Remote Functionalization
12.2.3 Electrochemical Remote Functionalizations
12.2.4 Carbene Insertion into CH Bonds
12.3 Reactions Occurring via Formation of Metal–Carbon Bonds
12.3.1 Pt‐Based Shilov Chemistry
12.3.2 Rh‐ and Ir‐Catalyzed C–H Borylation of (Functionalized) Alkanes
12.4 Altering Innate Reactivity by Polarity Reversal Strategies
12.4.1 Remote Functionalization of Aliphatic Amines via Quaternary Ammonium Salts
12.4.2 Remote Functionalization of Alcohols and Amides via Hydrogen Bond Interactions
Acknowledgments
References
13 Remote Oxidation of Aliphatic CH Bonds with Biologically Inspired Catalysts
13.1 Introduction. 13.1.1 Bioinspired Catalysis as a Tool for Site Selective CH Bond Oxidation
13.1.2 Typology of Bioinspired Catalysts
13.1.3 Site Selectivity in Aliphatic C–H Oxidation: Basic Considerations
13.2 Innate Substrate Based Aspects Governing Site Selectivity in C–H Oxidations
13.2.1 CH Bond Strength
13.2.2 Electronic Effects
13.2.3 Steric Effects
13.2.4 Directing Groups
13.2.5 Stereoelectronic Effects. 13.2.5.1 Hyperconjugation Effects
13.2.5.2 Strain Release and Torsional Effects
13.2.6 Chirality
13.3 Remote Oxidations by Reversal of Polarity. 13.3.1 Remote Oxidation in Amine Containing Substrates by Protonation of the Amine Site
13.3.2 Remote Oxidation of Amide Containing Substrates by Methylation of the Amide Moiety
13.3.3 Remote Oxidation via Polarity Reversal Exerted by Fluorinated Alcohol Solvents
13.4 Remote Oxidations Guided by Supramolecular Recognition
13.4.1 Lipophilic Interactions
13.4.2 Lipophilic Recognition by Cyclodextrins
13.4.3 Ligand to Metal Coordination
13.4.4 Hydrogen Bonding
13.5 Selective Aliphatic C–H Oxidation at Dicopper Complexes
13.6 Conclusions
References
Index
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