Remote C-H Bond Functionalizations

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)( t Bu) 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 p K avalues, 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(sp 3)–H functionalizati...Scheme 10.3 Palladium‐catalyzed γ‐C(sp 3)–H arylation of amino acids.Scheme 10.4 Palladium‐catalyzed γ‐C(sp 3)–H arylation of aliphatic carboxamid...Scheme 10.5 Quinoline‐ligand enabled palladium‐catalyzed arylation of γ‐C(spScheme 10.6 Palladium‐catalyzed γ‐C(sp 3)–H alkynylation of 3,3‐dimethylbutyi...Scheme 10.7 Palladium‐catalyzed γ‐C(sp 3)–H alkylation of L‐valine derivative...Scheme 10.8 Ligand‐enabled palladium‐catalyzed γ‐C(sp 3)–H olefination and ca...Scheme 10.9 Sequential γ‐C(sp 3)–H olefination and carboxylation.Scheme 10.10 Palladium‐catalyzed γ‐C(sp 3)–H alkenylation of carboxylic acids...Scheme 10.11 Palladium‐catalyzed γ‐C(sp 3)–H silylation and germanylation of ...Scheme 10.12 Palladium‐catalyzed γ‐C(sp 3)–H chalcogenation of carboxylic aci...Scheme 10.13 Palladium‐catalyzed γ‐C(sp 3)–H intramolecula amination.Scheme 10.14 Cobalt‐catalyzed γ‐benzyl C(sp 3)–H dehydrogenative amination....Scheme 10.15 Ligand‐enabled palladium‐catalyzed γ‐C(sp 3)–H arylation of N ‐Ph...Scheme 10.16 Palladium‐catalyzed γ‐C(sp 3)–H arylation of free aliphatic acid...Scheme 10.17 Palladium‐catalyzed γ‐C(sp 3)–H arylation of N ‐protected tert -le...Scheme 10.18 Palladium‐catalyzed intramolecular amination of C(sp 3) 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(sp 3)–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(sp 3)–H of alkyl amines via transient di...Scheme 10.31 Site‐selective alkenylation of δ‐C(sp 3) H bonds with alkynes vi...Scheme 10.32 Mechanistic experiments and proposed catalytic cycle.Scheme 10.33 Site‐selective δ‐C(sp 3)–H alkylation of amino acids and oligope...Scheme 10.34 Palladium‐catalyzed γ‐C(sp 3)–H arylation of a ketone enabled by...Scheme 10.35 Ligand‐enabled γ‐C(sp 3)–H arylation of aliphatic ketones [71]....Scheme 10.36 Ligand‐promoted γ‐C(sp 3)–H arylation of aliphatic aldehydes [35...Scheme 10.37 Site‐selective γ‐C(sp 3)–H arylation of alcohols with full sp 2c...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(sp 3)–H carbonylation.Scheme 10.41 Hemilabile benzyl ether directed distal C(sp 3)–H carbonylation ...