Читать книгу Remote C-H Bond Functionalizations - Группа авторов - Страница 4
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Оглавление1 Chapter 2Scheme 2.1 Directing template assisted meta‐CH bond functionalization. Rela...Scheme 2.2 Three categories of chelating functionality (CF). (a) N‐Based...Scheme 2.3 meta‐C–H activation of toluene derivatives.Scheme 2.4 meta‐C–H olefination of hydrocinnamic acid derivatives. Scheme 2.5 (a) 2‐hydroxybenzonitrile template assisted mono meta‐selective o...Scheme 2.6 (a) Proposed remote‐selective C‐H activation via κ2 coordination ...Scheme 2.7 (a) Rh(III)‐catalyzed directing template assisted remote meta‐C–H...Scheme 2.8 meta‐C–H arylation of hydrocinnamic acids with arylboronic ...Scheme 2.9 meta‐C–H arylation of hydrocinnamic acids with aryl iodides...Scheme 2.10 meta‐C–H olefination of phenylacetate.Scheme 2.11 meta‐C–H olefination of phenylacetic acid derivatives. Sou...Scheme 2.12 Rh‐catalyzed meta‐C–H olefination of phenylacetic acid der...Scheme 2.13 Pyridine‐based template assisted meta‐C–H olefination of p...Scheme 2.14 (a) meta‐C‐H perfluoroalkenylation of phenylacetic acid derivati...Scheme 2.15 Pyridine‐based template assisted meta‐C–H arylation and io...Scheme 2.16 (a) meta‐C–H deuteration of phenylacetic acid derivatives ...Scheme 2.17 (a) meta‐C–H olefination of benzoic acids. (b) Removal of direct...Scheme 2.18 (a) meta‐C–H acetoxylation of benzoic acids. (b) Elaboration of Scheme 2.19 meta‐C–H olefination of benzoic acid derivatives with conf...Scheme 2.20 meta‐C–H olefination of aniline derivatives.Scheme 2.21 (a) synthesis of substrate from CO2 for meta‐C–H activatio...Scheme 2.22 meta‐C–H olefination of tertiary anilines.Scheme 2.23 (a) meta‐C–H acetoxylation of aniline amides. (b) meta‐...Scheme 2.24 meta‐C–H acetoxylation of benzylamine derivatives. Scheme 2.25 meta‐C–H olefination of tertiary benzylamines and distal a...Scheme 2.26 meta‐C–H olefination of phenylethylamine derivatives.Scheme 2.27 Sequential remote‐selective regiodivergent C–H olefination of 2‐...Scheme 2.28 (a) Conformation promoted meta‐selective activation. (b) meta‐...Scheme 2.29 (a) meta‐C–H olefination of indoline derivatives. (b) Remo...Scheme 2.30 meta‐C–H arylation of indoline derivatives.Scheme 2.31 meta‐C–H acetoxylation of indoline derivatives.Scheme 2.32 meta‐C–H olefination of N‐heterocycles.Scheme 2.33 meta‐C–H olefination of 3‐phenylpyridines.Scheme 2.34 meta‐C–H olefination of 3‐phenylpyridines using nitrile‐ba...Scheme 2.35 (a) meta‐C–H olefination of benzylsulfonic acid derivative...Scheme 2.36 (a) meta‐C–H olefination of 2‐phenethylsulfonic acid deriv...Scheme 2.37 meta‐C–H olefination and alkylation of benzylsulfonyl and ...Scheme 2.38 meta‐C–H olefination and acetoxylation of benzylsulfonyl e...Scheme 2.39 Rh‐catalyzed meta‐C–H olefination of benzylsulfonyl esters...Scheme 2.40 meta‐C–H perfluoroalkenylation of benzylsulfonyl esters....Scheme 2.41 meta‐C–H allylation of benzylsulfonyl esters.Scheme 2.42 meta‐C–H oxygenation of benzylsulfonyl esters.Scheme 2.43 meta‐C–H cyanation of benzylsulfonyl and 2‐phenethylsulfon...Scheme 2.44 meta‐C–H deuteration of benzylsulfonyl esters.Scheme 2.45 meta‐C–H silylation and germanylation.Scheme 2.46 meta‐C–H olefination of phenol derivatives.Scheme 2.47 Organosilicon template assisted meta‐C–H olefination of ph...Scheme 2.48 Rh(III)‐catalyzed meta‐C–H olefination of phenol derivativ...Scheme 2.49 (a) meta‐selective C–H olefination of phenols. (b) Nickel‐cataly...Scheme 2.50 meta‐C–H olefination of 2‐phenyl phenol derivatives.Scheme 2.51 meta‐C–H olefination of benzyl alcohols. Scheme 2.52 meta‐C–H olefination of benzyl and phenyl ethyl alcohols.Scheme 2.53 meta‐C–H iodination of benzyl and phenylethyl alcohols.Scheme 2.54 meta‐C–H olefination of distal arene‐tethered alcohols.Scheme 2.55 meta‐C–H functionalizations of arenes with different linker leng...Scheme 2.56 Removal of the pyrimidine‐based template.Scheme 2.57 meta‐C–H allylation of alcohol derivatives.Scheme 2.58 meta‐C–H olefination of arene‐tethered diols.Scheme 2.59 meta‐C–H deuteration of alcohols.Scheme 2.60 meta‐C–H olefination of benzyl silanes.Scheme 2.61 (a) meta‐C–H cyanation of benzyl silanes. (b) Application of met...Scheme 2.62 meta‐C–H functionalizations of phosphonates.Scheme 2.63 meta‐C–H alkylation of phosphonates.Scheme 2.64 meta‐C–H deuteration of phosphonates.Scheme 2.65 Proposed catalytic cycle for meta‐C–H olefination.Scheme 2.66 Proposed transition state through computational study.
2 Chapter 3Scheme 3.1 Catellani's initial report on C–H functionalization of iodoarenes...Scheme 3.2 Proposed catalytic cycle for the ortho‐C–H alkylation of aryl iod...Scheme 3.3 ortho‐C–H alkylation of ortho‐substituted iodoarenes under Pd/NBE...Scheme 3.4 Lautens' modified reaction conditions for ortho‐C–H alkylation of...Scheme 3.5 Pd(II)‐initiated C–H functionalization of arenes under Pd/NBE cat...Scheme 3.6 ortho‐Alkylation of ortho‐unsubstituted iodoarenes with two diffe...Scheme 3.7 ortho‐C–H trifluoroethylation iodoarenes with trifluoroethyl iodi...Scheme 3.8 ortho‐Alkylation with racemic secondary alkyl iodides.Scheme 3.9 ortho‐Alkylation with enantioenriched secondary alkyl iodides.Scheme 3.10 Asymmetric ortho‐alkylation of iodoarenes under Pd/NBE catalysis...Scheme 3.11 Recent work on ortho‐alkylation reactions using various terminat...Scheme 3.12 ortho‐Alkylation/ipso‐alkynylation reactions using terminal alky...Scheme 3.13 Total synthesis of (+)‐linoxepin using ortho‐alkylation/ipso‐Hec...Scheme 3.14 ortho‐Alkylation/ipso‐heteroarylation of iodoarenes with heteroa...Scheme 3.15 ortho‐Alkylation using bifunctional alkylating reagents under Pd...Scheme 3.16 ortho‐Alkylation of iodoarenes containing terminating functional...Scheme 3.17 ortho‐Alkylation of simple iodoarenes with alkyne‐tethered alkyl...Scheme 3.18 Pd/NBE‐catalyzed reactions of iodoarenes with aryl‐substituted 2Scheme 3.19 Pd/NBE‐catalyzed reactions of iodoarenes with aziridines.Scheme 3.20 Pd/NBE‐catalyzed reactions of iodoarenes with epoxides.Scheme 3.21 Pd/NBE‐catalyzed homocoupling of 4‐fluorobromobenzene.Scheme 3.22 Pd/NBE‐catalyzed homocoupling of ortho‐substituted iodoarenes....Scheme 3.23 Pd/NBE‐catalyzed cross‐coupling of iodoarenes with electron‐poor...Scheme 3.24 ortho‐Arylation of iodoarenes using o‐bromophenols and 1‐bromo‐2...Scheme 3.25 ortho‐Arylation of iodoarenes using bromoarenes with N‐containin...Scheme 3.26 ortho‐Arylation of iodoarenes using bifunctional aryl halides.Scheme 3.27 ortho‐Arylation of iodoarenes using o‐bromophenols.Scheme 3.28 ortho‐Arylation of bifunctional iodoarenes under Pd/NBE catalysi...Scheme 3.29 Theoretical investigation on the origin of the “ortho effect.”...Scheme 3.30 Deviation from the “ortho effect.”Scheme 3.31 Overcoming the “ortho effect” in ortho‐arylation reactions by us...Scheme 3.32 ortho‐Acylation of aryl iodides using pre‐formed or in situ gene...Scheme 3.33 ortho‐Acylation of aryl iodides using norbornene derivatives as ...Scheme 3.34 ortho‐Acylation of aryl iodides using other types of terminating...Scheme 3.35 ortho‐Acylation of aryl iodides using bifunctional acylation rea...Scheme 3.36 Synthesis of benzo‐fused cyclic ketones and natural products usi...Scheme 3.37 ortho‐Alkoxycarbonylation of aryl iodides under Pd/NBE catalysis...Scheme 3.38 Dong's initial report on ortho‐amination of iodoarenes with N‐be...Scheme 3.39 ortho‐Amination of iodoarenes using N‐benzoyloxyamines in the pr...Scheme 3.40 ortho‐Amination of aryl bromides using N‐benzoyloxyamines. Scheme 3.41 ortho‐Amination of iodoarenes containing a terminating functiona...Scheme 3.42 ortho‐Amination of ortho‐unsubstituted iodoarenes using bridgehe...Scheme 3.43 Application of ortho‐amination/ipso‐alkynylation of iodoarenes i...Scheme 3.44 ortho‐Thiolation of iodoarenes using thiosulfonates as the thiol...Scheme 3.45 Pd(II)‐catalyzed C2‐functionalization of indoles.Scheme 3.46 Proposed mechanism for the Pd(II)‐catalyzed C2‐functionalization...Scheme 3.47 Synthetic applications of the Pd(II)‐catalyzed 2‐alkylation of i...Scheme 3.48 Pd(II)‐catalyzed 2‐alkylation of pyrroles.Scheme 3.49 Pd(II)‐catalyzed 2‐trifluoroethylation of indoles.Scheme 3.50 Pd(II)‐catalyzed meta‐C–H alkylation and arylation of arenes bea...Scheme 3.51 Pd(II)‐catalyzed meta‐C–H functionalization of arenes bearing an...Scheme 3.52 Pd(II)‐catalyzed enantioselective meta‐C–H functionalization of ...Scheme 3.53 Pd(II)‐catalyzed ortho alkylation of arylboronic acids or esters...Scheme 3.54 Pd(II)‐catalyzed ortho arylation of arylboronic esters.Scheme 3.55 Pd(II)‐catalyzed ortho acylation and amination of aryl boroxines...
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 1 with 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 85 under 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 96 under 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 sp3 CH 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 site‐selective C(sp3)–H functionalizati...Scheme 10.3 Palladium‐catalyzed γ‐C(sp3)–H arylation of amino acids.Scheme 10.4 Palladium‐catalyzed γ‐C(sp3)–H arylation of aliphatic carboxamid...Scheme 10.5 Quinoline‐ligand enabled palladium‐catalyzed arylation of γ‐C(spScheme 10.6 Palladium‐catalyzed γ‐C(sp3)–H alkynylation of 3,3‐dimethylbutyi...Scheme 10.7 Palladium‐catalyzed γ‐C(sp3)–H alkylation of L‐valine derivative...Scheme 10.8 Ligand‐enabled palladium‐catalyzed γ‐C(sp3)–H olefination and ca...Scheme 10.9 Sequential γ‐C(sp3)–H olefination and carboxylation.Scheme 10.10 Palladium‐catalyzed γ‐C(sp3)–H alkenylation of carboxylic acids...Scheme 10.11 Palladium‐catalyzed γ‐C(sp3)–H silylation and germanylation of ...Scheme 10.12 Palladium‐catalyzed γ‐C(sp3)–H chalcogenation of carboxylic aci...Scheme 10.13 Palladium‐catalyzed γ‐C(sp3)–H intramolecula amination.Scheme 10.14 Cobalt‐catalyzed γ‐benzyl C(sp3)–H dehydrogenative amination....Scheme 10.15 Ligand‐enabled palladium‐catalyzed γ‐C(sp3)–H arylation of N‐Ph...Scheme 10.16 Palladium‐catalyzed γ‐C(sp3)–H arylation of free aliphatic acid...Scheme 10.17 Palladium‐catalyzed γ‐C(sp3)–H arylation of N‐protected tert-le...Scheme 10.18 Palladium‐catalyzed intramolecular amination of C(sp3)H bonds ...Scheme 10.19 Construction of polycyclic nitrogen-containing heterocycles vi...Scheme 10.20 Palladium‐catalyzed oxalyl amide directed δ‐C–H amination of al...Scheme 10.21 Palladium‐catalyzed methylation of bicyclic amine with bidentat...Scheme 10.22 Palladium‐catalyzed remote arylation of anti‐influenza virus A ...Scheme 10.23 Arylation of alkyl picolinamides via Pd‐catalyzed remote C–H ac...Scheme 10.24 Palladium‐catalyzed remote δ‐arylation of various amines with d...Scheme 10.25 Iterative (hetero)arylation of aliphatic amines.Scheme 10.26 Palladium‐catalyzed remote ɛ‐C(sp3)–H alkynylation of alkyl ami...Scheme 10.27 Palladium‐catalyzed remote δ‐arylation of anilines assisted by ...Scheme 10.28 Stoichiometric formation and isolation of C–H cyclopalladation ...Scheme 10.29 Palladium‐catalyzed native directed remote δ‐arylation of free ...Scheme 10.30 Palladium‐catalyzed δ‐C(sp3)–H of alkyl amines via transient di...Scheme 10.31 Site‐selective alkenylation of δ‐C(sp3)H bonds with alkynes vi...Scheme 10.32 Mechanistic experiments and proposed catalytic cycle.Scheme 10.33 Site‐selective δ‐C(sp3)–H alkylation of amino acids and oligope...Scheme 10.34 Palladium‐catalyzed γ‐C(sp3)–H arylation of a ketone enabled by...Scheme 10.35 Ligand‐enabled γ‐C(sp3)–H arylation of aliphatic ketones [71]....Scheme 10.36 Ligand‐promoted γ‐C(sp3)–H arylation of aliphatic aldehydes [35...Scheme 10.37 Site‐selective γ‐C(sp3)–H arylation of alcohols with full sp2 c...Scheme 10.38 Synthesis of six‐membered palladacycles via competition experim...Scheme 10.39 Design of the tridentate directing group for remote C–H activat...Scheme 10.40 Proposed catalytic cycle for C(sp3)–H carbonylation.Scheme 10.41 Hemilabile benzyl ether directed distal C(sp 3 )–H carbonylation ...
10 Chapter 11Scheme 11.1 Radical‐mediated distal C(sp3)–H functionalization.Scheme 11.2 Selected milestones in radical‐mediated distal C(sp3)–H function...Scheme 11.3 sp2 carbon radical promoted hydrogen transfer.Scheme 11.4 Aryl radical guided desaturation of remote aliphatic CH bond wi...Scheme 11.5 Visible‐light photoredox catalyzed remote hydroxylation of aliph...Scheme 11.6 Aryl diazonium initiated remote C(sp3)–H functionalization.Scheme 11.7 Photoinduced Pd‐catalyzed desaturation of C(sp3)H bonds.Scheme 11.8 Radical arylation of inactive secondary/tertiary C(sp3)H bonds ...Scheme 11.9 (a) KO t Bu promoted carbon–carbon coupling of remote tertiary C(s...Scheme 11.10 Hydrogen‐atom transfer of hybrid vinyl palladium radical interm...Scheme 11.11 Regioselective vinylation of remote unactivated C(sp3)H bonds....Scheme 11.12 Total synthesis of Leuconoxine, Melodinine E, and Mersicarpine ...Scheme 11.13 Enantioselective C(sp3)H bond functionalization via 1,5‐HAT....Scheme 11.14 Alkyl radical guided C–H desaturation of aliphatic alcohols.Scheme 11.15 Catalytic iodine‐mediated Hofmann–Loffler reaction.Scheme 11.16 Catalytic bromine‐mediated Hofmann–Loffler reaction.Scheme 11.17 Triiodide‐mediated δ‐amination of inert CH bonds.Scheme 11.18 Visible‐light‐induced photoredox catalyzed Hofmann–Loffler reac...Scheme 11.19 Generation of nitrogen radical by reductive cleavage of CF bon...Scheme 11.20 Metal‐catalyzed C–H amination with organic azides.Scheme 11.21 Remote C(sp3)–H functionalization via radical initiated decompo...Scheme 11.22 Copper‐catalyzed remote C(sp3)–H azidation of benzohydrazides....Scheme 11.23 Photoredox 1,5‐H transfer of iminyl radicals.Scheme 11.24 Oxidative cleavage of α‐imino‐oxy acid based oxime to generate ...Scheme 11.25 Generation of nitrogen radicals by oxidation of NH bonds. (a) ...Scheme 11.26 Generation of nitrogen radicals by abstraction of hydrogen.Scheme 11.27 Electrochemical mediated generation of nitrogen radical.Scheme 11.28 Generation of oxygen radicals from N‐alkoxyphthalimides by phot...Scheme 11.29 Enantioselective functionalization of remote C(sp3)H bonds....Scheme 11.30 Photoredox catalyzed radical translocation of N‐alkoxypyridiniu...Scheme 11.31 Dual copper/photoredox catalyzed remote C(sp3)–H functionalizat...Scheme 11.32 Generation of oxygen radicals by Fe(II) catalyzed reduction of ...Scheme 11.33 Cascade of 1,5‐HAT and 1,4‐heteroaryl migration.Scheme 11.34 Oxygen radical directed heteroarylation of remote C(sp3)H bond...Scheme 11.35 Redox neutral remote C(sp3)H bond animation.
11 Chapter 12Scheme 12.1 Examples of TFDO oxidations at tertiary and secondary C–H positi...Scheme 12.2 Selectivity of dioxirane C–H oxidation in steroid derivatives.Scheme 12.3 Basic mechanisms of decatungstate photocatalysis, and representa...Scheme 12.4 TBADT‐catalyzed remote C–H fluorination of aliphatic esters with...Scheme 12.5 Decatungstate‐catalyzed C–H fluorination and 18F‐fluorination of...Scheme 12.6 Comparison of selectivity for different C–H fluorination methods...Scheme 12.7 Decatungstate‐catalyzed CC bond formation in aliphatic nitriles...Scheme 12.8 Decatungstate‐catalyzed CC bond formation in aliphatic ketones ...Scheme 12.9 Influence of steric and electronic effects on the regioselectivi...Scheme 12.10 Electrochemical aerobic oxidation of remote CH bonds.Scheme 12.11 Electrochemical fluorination of remote CH bonds.Scheme 12.12 General mechanism of the metal‐catalyzed carbene insertion.Scheme 12.13 Examples of catalyst‐dependent site selectivity in the insertio...Scheme 12.14 Examples of catalysts employed for the insertion of carbenes in...Scheme 12.15 Examples of selective carbene insertion into unactivated second...Scheme 12.16 Examples of selective carbene insertion into unactivated tertia...Scheme 12.17 Examples of selective carbene insertion into unactivated primar...Scheme 12.18 RhCp*‐catalyzed selective borylation of primary, non‐hindered C...Scheme 12.19 General mechanism for the Rh‐catalyzed C–H borylation of alkane...Scheme 12.20 Selectivity among different primary CH bonds in Rh‐ and Ir‐cat...Scheme 12.21 Selective borylation of secondary β CH bonds in cyclic ethers....Scheme 12.22 Ir‐catalyzed borylation of secondary CH bonds in cyclopropanes...Scheme 12.23 Activation and deactivation of CH bonds via polarity reversal ...Scheme 12.24 Comparison of BDE values and/or ΔG values for HAT of CH bonds ...Scheme 12.25 Example of selectivity of C–H oxidation in aliphatic amines und...Scheme 12.26 Oxidation of remote tertiary and secondary CH bonds in aliphat...Scheme 12.27 Oxidation of remote primary CH bonds in aliphatic amines via P...Scheme 12.28 Oxidation of remote benzylic CH bonds in aliphatic amines usin...Scheme 12.29 Remote C–H oxidation of aliphatic amines using Fe(PDP) complexe...Scheme 12.30 Oxidation of remote tertiary and secondary CH bonds in aliphat...Scheme 12.31 Supramolecular interaction between Mn(PDP–BC) and long‐chain al...Scheme 12.32 Photochemical decatungstate‐catalyzed oxidation of remote secon...Scheme 12.33 CC bond formation via amine protonation and radical addition‐t...Scheme 12.34 Effect of hydrogen bond donor HFIP on the selectivity of oxidat...Scheme 12.35 Effect of hydrogen bond donor HFIP on the selectivity of oxidat...
12 Chapter 13Scheme 13.1 Representative selective C–H oxidations taking place in nature....Scheme 13.2 Basic mechanistic scheme of C–H oxidation by mononuclear iron en...Scheme 13.3 Basic typology of C–H oxidation catalysts discussed in this chap...Scheme 13.4 Relative reactivity of CH bonds against HAT agents on the basis...Scheme 13.5 (a) Effect of EWGs on site‐selectivity in the oxidation tertiary...Scheme 13.6 Catalyst dependent selectivity based in sterics. (a) Oxidation o...Scheme 13.7 Carboxylic acid directed C–H oxidation compared with oxidation o...Scheme 13.8 Stereoelectronic effects in C–H oxidation reactions. (a) Catalyt...Scheme 13.9 (a) Strain release in C–H oxidations of 1,2‐dimethyl substituted...Scheme 13.10 Chirality dependent site selectivity in the oxidation of trans‐...Scheme 13.11 Protonation or complexation driven remote CH bond oxidation of...Scheme 13.12 Remote oxidation in amide and imide containing substrates.Scheme 13.13 Schematic representation of the HAT reaction of a methylenic si...Scheme 13.14 Catalytic hydroxylation of methylenes in HFIP. Values in italic...Scheme 13.15 Comparative chemoselective C–H oxidation in alcohol and ether c...Scheme 13.16 Comparative chemoselective C–H oxidation in amide and amine con...Scheme 13.17 Oxidation of cholesterol governed by lipophilic interactions.Scheme 13.18 Geometry control in the oxidation of an androstenediol derivati...Scheme 13.19 Control of selectivity by metal to ligand binding. (a) Metallop...Scheme 13.20 Kemps triacid appended supramolecular catalyst and envisioned i...Scheme 13.21 Competitive oxidation of a cis/trans mixture of S7.Scheme 13.22 Stereoselective C–H oxidation driven by recognition: enantiotop...Scheme 13.23 Distribution of ketone products formed upon oxidation of linear...Scheme 13.24 Selective oxidation of diamines by a supramolecular porphyrin c...Scheme 13.25 Schematic diagram of the selective oxidation of steroidal molec...
