Remote C-H Bond Functionalizations

3 Chapter 4Scheme 4.1 Directing group assisted site‐selective C–H functionalization of ...Scheme 4.2 Proposed catalytic cycle of directing group assisted meta ‐C–H fun...Scheme 4.3 meta ‐C–H alkylation of phenylacetic amide derivatives with NBE....Scheme 4.4 meta ‐C–H alkylation of phenylacetic amide derivatives with Yu‐med...Scheme 4.5 meta ‐C–H alkylation of benzylsulfonamide derivatives.Scheme 4.6 meta ‐C–H alkylation of nosyl‐protected methyl ester of phenylalan...Scheme 4.7 meta ‐C–H arylation of phenylacetic amide derivatives with NBE....Scheme 4.8 meta ‐C–H arylation of phenylacetic amide derivatives with Yu‐medi...Scheme 4.9 meta ‐C–H arylation of β‐arylethylamine derivatives.Scheme 4.10 meta ‐C–H arylation of biaryl‐2‐trifluoroacetamide derivatives....Scheme 4.11 meta ‐C–H arylation of nosyl‐protected aryl ethylamine, phenylgly...Scheme 4.12 meta ‐C–H arylation of benzylsulfonamide derivatives.Scheme 4.13 meta ‐C–H arylation of benzyl amine derivatives.Scheme 4.14 meta ‐C–H arylation of aniline, heterocyclic aromatic amine, phen...Scheme 4.15 (a) meta ‐C–H arylation of benzylamine derivatives. (b) Synthetic...Scheme 4.16 meta ‐C–H arylation of masked aromatic aldehyde derivatives.Scheme 4.17 (a) meta ‐C–H arylation of benzyl alcohol derivatives. (b) Cleava...Scheme 4.18 meta ‐C–H arylation of free phenylacetic acids.Scheme 4.19 (a) meta ‐C–H chlorination of aniline and phenol derivatives. (b)...Scheme 4.20 meta ‐C–H chlorination of benzylamine derivative.Scheme 4.21 meta ‐C–H amination of aniline and phenol derivatives.Scheme 4.22 meta ‐C–H amination of benzylamine and masked aromatic aldehyde d...Scheme 4.23 meta ‐C–H alkynylation of aniline derivatives.Scheme 4.24 (a) Enantioselective meta ‐C–H activation. (b) Enantioselective m ...

4 Chapter 5Figure 5.1 Strategies for remote meta ‐/ para ‐selective C–H activation. (a) St...Scheme 5.1 Ruthenium catalysis for C–H alkylation with n ‐hexyl bromide. (a) ...Scheme 5.2 Remote meta ‐C–H alkylations with secondary alkyl halides. (a) Sco...Scheme 5.3 meta ‐C–H Alkylations with tertiary alkyl halides. (a) Reactions o...Scheme 5.4 Proposed catalytic cycle for remote C–H alkylations via ortho ‐rut...Scheme 5.5 Remote meta ‐C–H alkylation with transformable/removable directing...Scheme 5.6 Remote meta ‐C–H alkylation with removable directing groups. (a) m ...Scheme 5.7 Ruthenium‐catalyzed meta ‐C–H mono‐ and difluoromethylations. (a) ...Scheme 5.8 Remote C–H alkylations with α‐bromocarbonyl compounds. (a) Ruthen...Scheme 5.9 Proposed catalytic cycle for the synergistic ruthenium‐phosphine ...Scheme 5.10 Remote C–H alkylations using an arene‐ligand‐free ruthenium comp...Scheme 5.11 Photo‐induced ruthenium‐catalyzed meta ‐C–H alkylations with alky...Scheme 5.12 Remote meta ‐C–H alkylations under visible light irradiation.Scheme 5.13 Oxidative ruthenium‐catalyzed meta ‐benzylation with toluene deri...Scheme 5.14 Site‐selectivity switch for ruthenium‐catalyzed C–H benzylation....Scheme 5.15 Proposed catalytic cycle for remote meta ‐C–H benzylations. Sourc...Scheme 5.16 Ruthenium‐catalyzed remote C–H carboxylation.Scheme 5.17 Remote C–H acylation via oxidative decarboxylation. Scheme 5.18 meta ‐C–H Sulfonylations of phenylpyridines 1with sulfonyl chlor...Scheme 5.19 Proposed catalytic cycle for meta ‐sulfonylation. Source: Modifie...Scheme 5.20 Azoarene‐directed meta ‐sulfonation.Scheme 5.21 Ruthenium‐catalyzed meta ‐bromination. (a) meta ‐Bromination with ...Scheme 5.22 Homogeneous or heterogeneous ruthenium catalysts for meta ‐bromin...Scheme 5.23 Ruthenium‐catalyzed meta ‐halogenation. (a) meta ‐Halogenation wit...Scheme 5.24 Ruthenium‐catalyzed meta ‐nitration.Scheme 5.25 Proposed catalytic cycle for ruthenium‐catalyzed meta ‐nitration....Scheme 5.26 Ruthenium‐catalyzed remote C–H nitration. (a) meta ‐C–H Nitration...Scheme 5.27 Oxidative C–H/C–H activation for para ‐selective alkylations.Scheme 5.28 para ‐C–H Oxygenations of anisoles 85under ruthenium catalysis....Scheme 5.29 Ruthenium‐catalyzed para ‐C–H alkylations with α‐bromo esters. (a...Scheme 5.30 Ruthenium‐catalyzed para ‐C–H mono‐ and difluoroalkylations. (a) ...Scheme 5.31 para ‐C–H Sulfonylations of pyridines 96under ruthenium catalysi...Scheme 5.32 Sequential meta ‐C–H alkylation/ ortho ‐C–H functionalizations in a...Scheme 5.33 meta ‐C–H Sulfonylation/ ortho ‐C–H chlorination of phenoxypyridine...

5 Chapter 6Figure 6.1 Site‐selective sp 3C H bond oxidation using Mn‐based catalysts: (...Figure 6.2 Development progression of iridium‐catalyzed borylation of arenes...Figure 6.3 Mechanism of iridium‐catalyzed borylation of arenes, as proposed ...Figure 6.4 Considerations concerning the regioselectivity of iridium‐catalyz...Figure 6.5 Examples of ortho ‐selective borylation using non‐covalent interac...Figure 6.6 Kuninobu, Kanai, and coworkers' meta ‐selective borylation using b...Figure 6.7 Kuninobu, Kanai, and coworkers' urea containing ligand modificati...Figure 6.8 Sulfonated bipyridine ligands developed within the Phipps group, ...Figure 6.9 Extending the chain length between the arene and ammonium groups ...Figure 6.10 Use of sulfonated bipyridine ligand to engage in hydrogen bond d...Figure 6.11 Substrates that present a competition between ion pair and hydro...Figure 6.12 Chattopadhyay's meta C–H borylation of amides: (a) reaction over...Figure 6.13 para C–H borylation by using an L‐shaped ligand: (a) reaction ov...Figure 6.14 Use of a bulky cation to disfavor borylation at the meta positio...Figure 6.15 Phipps and coworkers' “steric shield” strategy to controlling pa ...Figure 6.16 Stepwise increase of cation size across the benzylsulfonate subs...Figure 6.17 Maleczka, Smith, and coworkers' strategy to controlling para ‐sel...

6 Chapter 7Scheme 7.1 The iridium‐catalyzed borylation developed by Maleczka, Smith, an...Scheme 7.2 The para‐selective Ir‐catalyzed borylation by Saito et al. [34]....Scheme 7.3 The Rh‐catalyzed silylation developed by Cheng and Hartwig [48]....Scheme 7.4 The Pd‐catalyzed imidation and aryl‐piperazine formation develope...Scheme 7.5 The arene C–H amination developed by Nicewicz and coworkers [10]....Scheme 7.6 Arene C–H aminations to form primary anilines by Togni, Carreira,...Scheme 7.7 The dirhodium catalyzed arene C–H amination by Falck and coworker...Scheme 7.8 The synthesis of primary anilines through Fe‐catalyzed aminations...Scheme 7.9 Oxidative aromatic oxygenation by Ritter and coworkers [69]. aRe...Scheme 7.10 Electrophilic aromatic fluorination by Ritter and coworkers [73]...Scheme 7.11 Nucleophilic 18F‐fluorination by Nicewicz, Li, and coworkers [74...Scheme 7.12 The non‐directed chlorination by Fuchs, Nagib, and coworkers [77...Scheme 7.13 The thiofluoromethylation of unactivated arenes by Iskra, Yi, an...Scheme 7.14 The C–H thianthrenation of arenes developed by Ritter and cowork...Scheme 7.15 The Au‐catalyzed oxidative arylation developed by Ball, Lloyd‐Jo...Scheme 7.16 First arene‐limited olefination developed by Yu and coworkers us...Scheme 7.17 Pd‐catalyzed arene‐limited olefinations with a 2‐pyridone ligand...Scheme 7.18 Direct C–H cyanation of arenes by Wang, Nicewicz, Gooßen, and co...Scheme 7.19 Pd‐catalyzed arene‐limited cyanations by Ritter, van Gemmeren, Y...