Remote C-H Bond Functionalizations. Группа авторов

chlorination of phenoxypyridine...

      5 Chapter 6Figure 6.1 Site‐selective sp³ C

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]. ^a Re...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...

      7 Chapter 8Scheme 8.1 Approaches for distal para‐C–H functionalizations. (a) DG assiste...Scheme 8.2 para‐Selective alkenylation of toluene scaffolds using D‐shaped t...Scheme 8.3 para‐Selective acetoxylation of toluene scaffolds using D‐shaped ...Scheme 8.4 para‐Selective alkenylation of phenols using D‐shaped template....Scheme 8.5 DG removal from para‐alkenylated product.Scheme 8.6 Optimization of DG and silylating reagent.Scheme 8.7 Scope of para‐silylation.Scheme 8.8 Plausible catalytic cycle for para‐silylation.Scheme 8.9 Scope of para‐ketonization.Scheme 8.10 Plausible catalytic cycle for para‐ketonization reaction.Scheme 8.11 Plausible hydrolysis pathways of para‐alkenylated ether (E).Scheme 8.12 para‐Selective acetoxylation of benzoic acid derivative.Scheme 8.13 Scope of para‐selective cyanation.Scheme 8.14 Rhodium catalyzed para‐selective alkenylation.Scheme 8.15 C4‐alkylation of pyridine in Ni/Al cooperative catalysis.Scheme 8.16 Plausible mechanism for C4‐alkylation of pyridine in Ni/Al coope...Scheme 8.17 Labeling experiment in C4‐alkylation of pyridine in Ni/Al cooper...Scheme 8.18 C4‐alkenylation of pyridine in Ni/Al cooperative catalysis.Scheme 8.19 Ni–Al bimetallic intermediate bridged by pyridine.Scheme 8.20 Plausible mechanism for C4‐alkenylation of pyridine in Ni/Al coo...Scheme 8.21 Scope of C4‐alkylation of benzamide and aromatic ketone in Ni/Al...Scheme 8.22 Labelling experiment for C4‐alkylation of benzamide in Ni/Al coo...Scheme 8.23 Plausible mechanism for C4‐alkylation of benzamide in Ni/Al coop...Scheme 8.24 para‐C–H alkylation of sulfonamides by Ni–Al co‐operative cataly...Scheme 8.25 para‐Borylation of amide in Ir/Al co‐operative catalysis.Scheme 8.26 C4‐borylation of pyridine in Ir/Al co‐operative catalysis.Scheme 8.27 Catalyst controlled para‐borylation of arenes.Scheme 8.28 Proposed L‐shaped template.Scheme 8.29 Scope of para‐borylation using L‐shaped template.Scheme 8.30 para‐C–H borylation using ion‐pair interaction by Smith's protoc...Scheme 8.31 para‐C–H borylation using ion‐pair interaction by Phipps protoco...

      8 Chapter 9Scheme 9.1 Innate electronic bias of indole based on resonance of pyrrole mo...Scheme 9.2 Seminal example of C–H functionalization of indole at unusual C4 ...Scheme 9.3 Palladium‐catalyzed highly C4‐selective C–H alkenylation of trypt...Scheme 9.4 Ruthenium‐catalyzed C4‐selective C–H alkenylation of 3‐formylindo...Scheme 9.5 Directing‐group‐controlled C4‐ and C2‐selective C–H alkenylation ...Scheme 9.6 Iridium‐catalyzed C4‐selective C–H amidation of 3‐carbonylindoles...Scheme 9.7 Palladium‐catalyzed C4‐selective C–H arylation of 3‐pivaloylindol...Scheme 9.8 Palladium‐catalyzed C4‐selective C–H trifluoroethylation of 3‐ace...Scheme 9.9 Rhodium‐catalyzed, coupling‐partner‐dependent C4‐ and C2‐selectiv...Scheme 9.10 Rhodium‐catalyzed C4‐selective C–H alkenylation of 3‐mercaptoind...Scheme 9.11 Site selectivity controlled by directing group on nitrogen: C2 v...Scheme 9.12 Iridium‐catalyzed C–H borylation of NH indoles. cod, 1,5‐cyclooc...Scheme 9.13 Iridium‐catalyzed C7‐selective C–H borylation of indoles.Scheme 9.14 Cp^*Rh(III)‐catalyzed, pivaloyl‐directed C7‐selective C–H alk...Scheme 9.15 Iridium‐catalyzed, pivaloyl‐directed C7‐selective C–H amidation ...Scheme 9.16 Palladium‐catalyzed C7‐selective C–H arylation and alkenylation ...Scheme 9.17 Rhodium‐catalyzed C7‐selective C–H arylation, alkenylation, acyl...Scheme 9.18 Copper‐catalyzed C5‐selective C–H arylation of 3‐pivaloylindoles...Scheme 9.19 Copper‐catalyzed, P(O)(tBu)₂‐directed C6‐selective C–H arylation...Scheme 9.20 Ruthenium‐catalyzed C6‐selective C–H alkylation of indoles with ...Scheme 9.21 Resonance, theoretical pK _a values, and early examples of α‐selec...Scheme 9.22 Palladium‐catalyzed β‐selective C–H arylation of thiophenes with...Scheme 9.23 Palladium‐catalyzed β‐selective C–H arylation of thiophenes with...Scheme 9.24 Palladium‐catalyzed β‐selective C–H arylation of (benzo)thiophen...Scheme 9.25 Directed C4‐selective C–H functionalization of benzothiophenes....Scheme 9.26 Rhodium‐ and iridium‐catalyzed β‐selective C–H borylation of N‐T...Scheme 9.27 Palladium‐catalyzed β‐selective C–H alkenylation of N‐TIPS pyrro...Scheme 9.28 Rhodium‐catalyzed β‐selective C–H arylation of pyrroles with ary...Scheme 9.29 Early examples of C2‐selective C–H functionalization of pyridine...Scheme 9.30 Palladium‐catalyzed C3‐selective C–H arylation of pyridines with...Scheme 9.31 Palladium‐catalyzed C3‐selective C–H alkenylation of pyridines w...Scheme 9.32 Palladium‐catalyzed directed C3‐selective C–H arylation of pyrid...Scheme 9.33 Palladium‐catalyzed, oxidant‐controlled C3‐ and C2‐selective deh...Scheme 9.34 Palladium‐catalyzed directed C4‐selective C–H arylation of pyrid...Scheme 9.35 Nickel/aluminum‐catalyzed C4‐selective C–H alkylation of pyridin...Scheme 9.36 Nickel/aluminum‐catalyzed C4‐selective C–H alkenylation of pyrid...Scheme 9.37 Iridium‐/aluminum‐catalyzed C4‐selective C–H borylation of pyrid...Scheme 9.38 Metal hydride‐catalyzed C4‐selective C–H alkylation of pyridines...Scheme 9.39 Early examples of C–H arylation of thiazoles at the C2 and/or C5...Scheme 9.40 Palladium‐catalyzed C4‐selective C–H arylation of thiazoles with...Scheme 9.41 Rhodium‐catalyzed C8‐selective C–H arylation of quinolines with ...Scheme 9.42 Iridium‐catalyzed C8‐selective C–H silylation of quinolines with...

      9 Chapter 10Scheme 10.1 Directing group assisted transition metal‐catalyzed C–H function...Scheme 10.2 Directed metal‐catalyzed