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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 C

H 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 C

C 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

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