Remote C-H Bond Functionalizations

10 Chapter 11Scheme 11.1 Radical‐mediated distal C(sp 3)–H functionalization.Scheme 11.2 Selected milestones in radical‐mediated distal C(sp 3)–H function...Scheme 11.3 sp 2carbon 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(sp 3)–H functionalization.Scheme 11.7 Photoinduced Pd‐catalyzed desaturation of C(sp 3) H bonds.Scheme 11.8 Radical arylation of inactive secondary/tertiary C(sp 3) H bonds ...Scheme 11.9 (a) KO tBu 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(sp 3) H bonds....Scheme 11.12 Total synthesis of Leuconoxine, Melodinine E, and Mersicarpine ...Scheme 11.13 Enantioselective C(sp 3) 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 C H bonds.Scheme 11.18 Visible‐light‐induced photoredox catalyzed Hofmann–Loffler reac...Scheme 11.19 Generation of nitrogen radical by reductive cleavage of C F bon...Scheme 11.20 Metal‐catalyzed C–H amination with organic azides.Scheme 11.21 Remote C(sp 3)–H functionalization via radical initiated decompo...Scheme 11.22 Copper‐catalyzed remote C(sp 3)–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 N H 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(sp 3) H bonds....Scheme 11.30 Photoredox catalyzed radical translocation of N ‐alkoxypyridiniu...Scheme 11.31 Dual copper/photoredox catalyzed remote C(sp 3)–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(sp 3) H bond...Scheme 11.35 Redox neutral remote C(sp 3) 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 C C 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 C H bonds.Scheme 12.11 Electrochemical fluorination of remote C H 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 C H bonds in Rh‐ and Ir‐cat...Scheme 12.21 Selective borylation of secondary β C H bonds in cyclic ethers....Scheme 12.22 Ir‐catalyzed borylation of secondary C H bonds in cyclopropanes...Scheme 12.23 Activation and deactivation of C H bonds via polarity reversal ...Scheme 12.24 Comparison of BDE values and/or Δ G values for HAT of C H bonds ...Scheme 12.25 Example of selectivity of C–H oxidation in aliphatic amines und...Scheme 12.26 Oxidation of remote tertiary and secondary C H bonds in aliphat...Scheme 12.27 Oxidation of remote primary C H bonds in aliphatic amines via P...Scheme 12.28 Oxidation of remote benzylic C H 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 C H 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 C C 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...