Читать книгу Methodologies in Amine Synthesis - Группа авторов - Страница 4

1 Chapter 1Scheme 1.1 General structure of electrophilic aminating reagent.Scheme 1.2 Mechanisms of two main types of electrophilic amination.Scheme 1.3 Early examples of Cu‐catalyzed electrophilic amination.Scheme 1.4 Cu‐catalyzed electrophilic amination of organozinc reagents.Scheme 1.5 Cu‐catalyzed electrophilic amination via aryne intermediate.Scheme 1.6 Cu‐catalyzed electrophilic amination of organolithium reagents.Scheme 1.7 Electrophilic amination of arylcuprates using a NH‐oxaziridine.Scheme 1.8 Electrophilic amination via directed C–H cupration.Scheme 1.9 Cu‐catalyzed electrophilic amination of arylboronates.Scheme 1.10 Cu‐catalyzed electrophilic amination of aryl silanes.Scheme 1.11 Cu‐catalyzed electrophilic amination of silyl enol ethers.Scheme 1.12 Cu‐catalyzed electrophilic catalyzed aminoboration of styrenes....Scheme 1.13 Cu‐catalyzed electrophilic hydroamination of styrenes.Scheme 1.14 Enantioselective Cu‐catalyzed electrophilic hydroamination of st...Scheme 1.15 Enantioselective Cu‐catalyzed electrophilic hydroamination of st...Scheme 1.16 Cu‐catalyzed electrophilic amination of alkynes.Scheme 1.17 Cu‐catalyzed annulative electrophilic amination.Scheme 1.18 Cu‐catalyzed electrophilic diamination.Scheme 1.19 Cu‐catalyzed electrophilic amino‐lactonization.Scheme 1.20 Cu‐catalyzed ring‐opening amination.Scheme 1.21 Cu‐catalyzed C–H amination of heterocycles.Scheme 1.22 Electrophilic amination catalyzed by other transition metals....Scheme 1.23 Pd‐catalyzed aromatic C–H amination via electrophilic amination....Scheme 1.24 Pd‐catalyzed aliphatic C–H amination via electrophilic amination...Scheme 1.25 Ru‐catalyzed C–H amination.Scheme 1.26 Pd‐catalyzed Catellani‐type C–H electrophilic amination.Scheme 1.27 Fe‐catalyzed electrophilic amination of styrenes.Scheme 1.28 Rh‐catalyzed formation of metallanitrenes.Scheme 1.29 Rh‐catalyzed NH‐aziridination of unactivated olefins using DPH....Scheme 1.30 Rh‐catalyzed NH‐aziridination of unactivated olefins using HOSA....Scheme 1.31 Rh‐catalyzed aromatic C–H amination.Scheme 1.32 Problems with uncatalyzed electrophilic amination.Scheme 1.33 TM‐free electrophilic amination of arylboronic acids.Scheme 1.34 TM‐free electrophilic amination of arylmetals using NH‐oxaziridi...Scheme 1.35 TM‐free Prilezhaev reaction.Scheme 1.36 TM‐free Rubottom oxidation.Scheme 1.37 TM‐free NH‐aziridination of unactivated olefins.

2 Chapter 2Scheme 2.1 Radical transposition processes using nitrogen radicals.Scheme 2.2 1,5‐HAT process in HLF reaction.Scheme 2.3 Geometrical factors, polar and enthalpic effects in 1,5‐HAT proce...Scheme 2.4 Photochemical intramolecular C(sp³)–H imination of tertiary aliph...Scheme 2.5 Photoinduced aminosulfonylation of C(sp³)—H bonds with sulfur dio...Scheme 2.6 Redox neutral remote functionalization of C(sp³)—H bonds via imin...Scheme 2.7 Intermolecular remote C(sp³)–H and C–C vinylations via iminyl rad...Scheme 2.8 Remote C(sp³)–H allyation of amides using organic photocatalyst....Scheme 2.9 Site‐selective remote C(sp³)–H heteroarylation of amides.Scheme 2.10 Visible‐light‐promoted C(sp³)–H amidation and chlorination of N‐...Scheme 2.11 Site‐specific intermolecular γ‐C(sp...Scheme 2.12 Nitrogen radical mediated remote functionalization of amides and...Scheme 2.13 Amide‐directed selective C—C bond formation at C(sp³)—H bonds....Scheme 2.14 Remote amide allylation using allyl chlorides and Ni(0) cocataly...Scheme 2.15 Regioselective cross‐coupling of C(sp³)—H bonds and alkyl bromid...Scheme 2.16 Iodine‐catalyzed visible‐light mediated C–H aminations.Scheme 2.17 Imidate radical mediated β‐C–H amination of alcohols.Scheme 2.18 Remote heteroarylation of amides via sulfonamidyl radicals [55]....Scheme 2.19 Site‐specific C–H functionalization via HAT using N‐dithiocarbam...Scheme 2.20 γ‐C(sp³)–H chlorination and...Scheme 2.21 Iron‐catalyzed remote C(sp³)–H azidation of ketones via iminyl a...Scheme 2.22 Amide‐directed fluorination of C—H bonds catalyzed by iron.Scheme 2.23 Copper‐catalyzed remote arylation of C(sp³)—H bonds via amidyl r...Scheme 2.24 Enantioselective remote C–H cyanation of amines via copper‐catal...

3 Chapter 3Scheme 3.1 C—N bond formation applying N—H bonds via photo/electrochemical m...Scheme 3.2 PCET‐mediated intramolecular carbo/hyrdroamination of alkenes....Scheme 3.3 PCET‐mediated intra/intermolecular amination of alkenes. (a) Hydr...Scheme 3.4 Electrocatalytic intramolecular hydroamination of alkenes.Scheme 3.5 Electrochemical synthesis of multifunctionalized (aza)indoles. RV...Scheme 3.6 Electrochemical intramolecular oxidative amination of tri‐ and te...Scheme 3.7 Electrochemical synthesis of imidazo‐fused N‐heteroaromatic compo...Scheme 3.8 Applying hydrazonyl radical for C—N bond formation in photochemis...Scheme 3.9 Visible‐light‐enabled access to phthalazine derivatives via an am...Scheme 3.10 Photocatalytic C—N bond formation for the preparation of N‐aryli...Scheme 3.11 Mechanistic proposal for the photocatalytic synthesis of N‐aryli...Scheme 3.12 Visible‐light‐initiated tandem reaction for the synthesis of fus...Scheme 3.13 Photocatalytic intramolecular hydroamination of olefins with ami...Scheme 3.14 Photocatalytic intermolecular hydroamination of unactivated olef...Scheme 3.15 Photocatalytic intermolecular anti‐Markovnikov hydroamination of...Scheme 3.16 Photoinduced, CuCl‐catalyzed oxidative C–N coupling of anilines ...Scheme 3.17 Proposed mechanism for the photoinduced, CuCl‐catalyzed C–N coup...Scheme 3.18 Visible‐light‐induced direct C–H amination of heteroarenes with ...Scheme 3.19 Visible‐light‐mediated C–H amination of heteroarenes.Scheme 3.20 Photocatalytic dehydrogenative C–H imidation of arenes with sulf...Scheme 3.21 Photocatalytic aryl C–H amination using primary aliphatic amines...Scheme 3.22 Anodic N—H bond cleavage for aromatic C—H bond amination.Scheme 3.23 Electrochemical oxidative C–H amination of phenols.Scheme 3.24 Site‐selective aromatic C–H amination via photoredox catalysis....Scheme 3.25 Photoinduced oxidant‐free C–H amination of arenes with azoles....Scheme 3.26 Selective C–H amination of electron‐rich arenes via photoredox c...Scheme 3.27 Electrochemical ortho‐amination of aromatic C—H bonds with azole...Scheme 3.28 Direct C2‐sulfonamidation of pyrroles via visible‐light photored...Scheme 3.29 DDQ‐mediated C2‐amination of thiophenes via visible‐light photor...Scheme 3.30 Photocatalytic benzene C–H amination and hydroxylation with hydr...Scheme 3.31 Anti‐Markovnikov hydroaminations of alkenes by two component org...Scheme 3.32 Photocatalytic dehydrogenative cross‐coupling of alkenes with az...Scheme 3.33 Photoinduced oxidative [4+2] imine/alkene annulation with H₂ lib...Scheme 3.34 Visible‐light‐enabled direct benzylic C(sp³)–H amination.Scheme 3.35 Benzylic C–H amination via visible‐light photoredox catalysis....Scheme 3.36 Electrochemical dehydrogenative imidation of N‐methyl‐substitute...Scheme 3.37 Electrochemical dehydrogenative imidation of N‐methyl substitute...Scheme 3.38 Light‐driven direct intramolecular C–N cross‐coupling.Scheme 3.39 Mechanistic proposal for the light‐driven direct intramolecular ...Scheme 3.40 Visible‐light‐promoted CDC amination of phenols and phenothiazin...Scheme 3.41 Visible‐light‐mediated CDC amination of phenols and acyclic diar...Scheme 3.42 Electro‐oxidative para‐selective C–H/N–H cross‐coupling with hyd...Scheme 3.43 Selective C–H amination of heteroarenes with azoles via an organ...Scheme 3.44 Electrochemical oxidative C–H/N–H cross‐couplings for C—N bond f...Scheme 3.45 Electro‐oxidative C–H azolation of phenol and aniline derivative...Scheme 3.46 Enantioselective amination via PCET followed by stereo‐controlle...Scheme 3.47 Electrochemical intermolecular oxidative C(sp³)–H/N–H cross‐coup...

4 Chapter 4Figure 4.1 Propargylamines: synthetic methods and drugs containing a proparg...Scheme 4.1 Chiral ligands used in asymmetric A³ coupling reactions.Scheme 4.2 Li's approach to the enantioselective synthesis of propargylamine...Scheme 4.3 Enantioselective A³ coupling approaches to propargylamines.Scheme 4.4 Knochel's enantioselective synthesis of propargylamines.Scheme 4.5 Proposed mechanism for the (R)‐(+)‐Quinap‐catalyzed A³ coupling....Scheme 4.6 Synthesis of propargylamines using (S)‐StackPhos ligand.Scheme 4.7 Aponick's strategy for the asymmetric synthesis of 3‐amino skippe...Scheme 4.8 Asymmetric synthesis of propargylamines using the StackPhim ligan...Scheme 4.9 Asymmetric synthesis of propargylamines using the UCD‐Phim L11....Scheme 4.10 Asymmetric synthesis of propargylamines using ligand L12.Scheme 4.11 Synthesis of propargylamines using Pybox ligands L13 and L14....Scheme 4.12 Proposed mechanism for the synthesis of propargylamines using Py...Scheme 4.13 Nishibayashi's approaches to propargylamines.Scheme 4.14 Hu's synthesis of propargylamines using chiral tridentate P,N,N ...Scheme 4.15 Use of a Ni(cod)₂/L19 complex in the asymmetric synthesis of pro...Scheme 4.16 Synthesis of propargylamines from ethynyl epoxides.Scheme 4.17 Asymmetric synthesis of propargylamines from lactones and cyclic...Scheme 4.18 Asymmetric synthesis of propargylamines from enamines.Scheme 4.19 Proposed mechanism for the CuBr/Quinap L6‐catalyzed synthesis of...Scheme 4.20 Synthesis of propargylamines via Rh/L23‐catalyzed enantioselecti...Scheme 4.21 Enantioselective hydrogenation of the alkynyl‐substituted enamid...Scheme 4.22 Chemoselective biomimetic hydrogenation of fluorinated alkynyl‐k...Scheme 4.23 Proposed mechanism for the reduction of ketimines.Scheme 4.24 Rhodium‐catalyzed hydrogenation of alkynyl–aryl hydrazones.Scheme 4.25 Synthesis of cyclic propargylamines via cobalt‐catalyzed intramo...Scheme 4.26 Mechanism of the cobalt‐catalyzed intramolecular cyclization.Scheme 4.27 Synthesis of chiral 2‐alkynyl‐indolines and chiral heterocyclic ...Scheme 4.28 Synthesis of cyclic propargylamines via intramolecular nitrene i...Scheme 4.29 CAL‐B‐catalyzed enzymatic kinetic resolution of 1‐aryl‐propargyl...Scheme 4.30 Enzymatic kinetic resolution of propargylamines using penicillin...Scheme 4.31 Synthesis of propargylamines using ω‐transaminases.Scheme 4.32 Synthesis of propargylamines through the combination of alcohol ...Scheme 4.33 Reductase‐biocatalyzed synthesis of propargylamines.Scheme 4.34 MAO‐N/Au chemoenzymatic synthesis of cyclic propargylamines.Scheme 4.35 Rueping's photoredox approach to propargylamines.Scheme 4.36 Photoredox synthesis of propargylamines using ethynylbenziodoxol...Scheme 4.37 Synthesis of propargylamines via photoredox decarboxylative alky...Scheme 4.38 Copper photoredox‐catalyzed A³ coupling of arylamines, terminal ...Scheme 4.39 Brønsted acid‐catalyzed Mannich‐type...Scheme 4.40 Organocatalyzed asymmetric Mannich‐type reaction of aldehydes wi...Scheme 4.41 syn‐Selective Mannich synthesis of propargylamines.Scheme 4.42 Asymmetric synthesis of syn‐propargylamines...Scheme 4.43 Synthesis of propargylamine via Friedel–Crafts‐type arylation.Scheme 4.44 Organocatalytic kinetic resolution of propargylamines. (a) Seide...Scheme 4.45 Organocatalytic reduction of alkynyl ketimines.Scheme 4.46 Synthesis of pyrroles from propargylamines.Scheme 4.47 Synthesis of pyrrolines from propargylamines.Scheme 4.48 Synthesis of pyridines from propargylamines.Scheme 4.49 Copper‐ and gold‐catalyzed synthesis of quinolines from propargy...Scheme 4.50 Synthesis of quinolines from N‐aryl‐propargylamines.Scheme 4.51 Synthesis of oxazoles from propargylamines.Scheme 4.52 Recent syntheses of oxazoles from propargylamides.Scheme 4.53 Reactions of propargylamine with CS₂.Scheme 4.54 Reactions of propargylamine with isothiocyanates.Scheme 4.55 Synthesis of thiazoline derivatives from N‐propargylamines using...

5 Chapter 5Scheme 5.1 General equation for the reductive amination of an aldehyde or a ...Scheme 5.2 Reductive amination of 2‐methyl‐6‐ethyl‐aniline and methoxyaceton...Scheme 5.3 Reductive amination of the ketone function to produce the chiral ...Scheme 5.4 Chiral bisphosphine‐thiourea ligand (ZhaoPhos ligand).Scheme 5.5 Intramolecular asymmetric reductive amination using [Ir(COD)Cl]₂/...Scheme 5.6 Synthesis of (S)‐rivastigmine from meta‐hydroxyacetophenone and d...Scheme 5.7 Asymmetric reductive amination under dynamic kinetic resolution c...Scheme 5.8 Reductive amination of alkyl aryl ketones catalyzed by [Ru(OAc)₂]...Scheme 5.9 The Knölker iron catalyst and the TRIP Brønsted acid.Scheme 5.10 Asymmetric reductive amination of 2‐methyl cyclopentanone and cy...Scheme 5.11 Asymmetric hydroamination of an unactivated alkene with a second...Scheme 5.12 Enantioselective hydroamination of 1‐octene with 1‐tert‐butylimi...Scheme 5.13 Proposed mechanism for the asymmetric hydroamination of (R)‐3‐pe...Scheme 5.14 (a) Enantioselective hydroamination of styrene catalyzed by the ...Scheme 5.15 Iridium‐catalyzed hydroamination of norbornene by 4‐bromoaniline...Scheme 5.16 Intramolecular hydroaminomethylation of 5‐hex‐1‐ene amines catal...Scheme 5.17 Asymmetric intramolecular hydroamination of 2,2,5‐triphenylpent‐...Scheme 5.18 Stereoselective synthesis of 2,5‐substituted pyrrolidines from c...Scheme 5.19 Synthesis of the enantiopure α‐arylpyrrolid...Scheme 5.20 Chiral aziridine synthesis catalyzed by a Cu–H/(S)‐DTBM‐SegPhos ...Scheme 5.21 Hydroaminoalkylation of a secondary amine through C=C bond forma...Scheme 5.22 Synthesis of the tantalum catalyst precursor in the hydroaminoal...Scheme 5.23 Main steps of the catalytic cycle calculated by DFT, showing the...Scheme 5.24 Intermolecular coupling of N‐methylaniline with...Scheme 5.25 Hydroaminomethylation reaction of olefins: synthesis of amines....Scheme 5.26 Rh‐catalyzed hydroaminomethylation of styrene using L1–L4 ...Scheme 5.27 Energy values for the hydrogenation of E‐ and Z‐enamines.Scheme 5.28 Dynamic kinetic reductive amination of aldehydes developed by Li...Scheme 5.29 Rh‐ and organocatalyzed asymmetric hydroaminomethylation of styr...Scheme 5.30 Improved system in the metal and organocatalyzed asymmetric HAM ...Scheme 5.31 Rh‐catalyzed asymmetric interrupted hydroaminomethylation of sty...Scheme 5.32 Rh‐catalyzed asymmetric hydroaminomethylation of...Scheme 5.33 Rhodium species observed in the Rh‐catalyzed asymmetric hydroami...Scheme 5.34 Asymmetric photoredox β‐amination of α,...

6 Chapter 6Scheme 6.1 Hajos–Parrish–Eder–Sauer–Wiechert reactions for the synthesis of ...Scheme 6.2 Alkylation of a substituted indanone 6 catalyzed by Cinchona alka...Scheme 6.3 Retrosynthetic approach for the synthesis of telcagepant.Scheme 6.4 Optimized organocatalytic asymmetric addition of nitromethane to ...Scheme 6.5 Retrosynthetic plan to obtain MK‐8613, by using asymmetric organo...Scheme 6.6 Enantioselective malonate addition to nitrostyrene 18 promoted by...Scheme 6.7 Retrosynthetic approach to funapide encompassing the organocataly...Scheme 6.8 Optimized enantioselective aldol reaction between 21 and formalde...Scheme 6.9 Retrosynthetic analysis of letermovir encompassing the key organo...Scheme 6.10 First‐generation enantioselective aza‐Michael cyclization based ...Scheme 6.11 Second‐generation enantioselective aza‐Michael cyclization based...Scheme 6.12 Possible transition states for the aza‐Michael reaction with H‐b...Scheme 6.13 Retrosynthetic approach for the synthesis of censavudine.Scheme 6.14 Synthesis of enantiopure pyranones 38 via a dynamic kinetic acyl...Scheme 6.15 Trapping of the furanose form 37′ with benzoic anhydride u...Scheme 6.16 Regio‐ and stereoselective (at P) introduction of the phosphoram...Scheme 6.17 Stereoselective phosphoramidate formation in uprifosbuvir synthe...Scheme 6.18 Pfizer manufacturing route to pregabalin encompassing an early‐s...Scheme 6.19 Retrosynthetic disconnections of the γ‐amino acid pregabalin.Scheme 6.20 Desymmetrization of glutaric anhydride 53 promoted by quinine 58Scheme 6.21 Synthesis of pregabalin and ent‐pregabalin by catalytic desymmet...Scheme 6.22 Enantioselective conjugate addition of cyanide to alkylidene mal...Scheme 6.23 Enantioselective addition of nitromethane to 74 catalyzed by entScheme 6.24 Synthesis of pregabalin on kilogram scale via enantioselective c...Scheme 6.25 Enantioselective additions of acetaldehyde to nitroalkene 56 und...Scheme 6.26 One‐pot synthesis of pregabalin by a “Michaelase” enantioselecti...Scheme 6.27 Simplified reaction pathway, intermediates, and transition state...Scheme 6.28 Addition of malonates to nitroalkene 56. Selected bifunctional c...Scheme 6.29 Downstream routes to pregabalin from catalytic product 87.Scheme 6.30 Typical preparation of nitroalkene 56 vs. flow chemistry approac...Scheme 6.31 Three‐component approach to 87 by the multisite hybrid catalyst Scheme 6.32 Enantioselective additions of Meldrum's acid to nitroalkene 56 c...Scheme 6.33 Telaprevir and synthetic approaches to its bicyclic amino acid c...Scheme 6.34 Synthesis of N‐benzyl telaprevir core 111 based on quinidine 103Scheme 6.35 Retrosynthetic approaches to the telaprevir core 98: desymmetriz...Scheme 6.36 Enantioselective approach to telaprevir core 98 by chiral masked...Scheme 6.37 PTC in enantioselective conjugate additions of benzophenone glyc...Scheme 6.38 PTC addition of benzophenone glycinate imine 122 with binaphthyl...Scheme 6.39 PTC addition of benzophenone imine glycinate 122 to 114 catalyze...Scheme 6.40 Alternative glycinate imine substrates 133 and 136 applied to th...Scheme 6.41 Aminocatalytic additions of 2‐amidomalonates 138 and 139 to cycl...Scheme 6.42 Aminocatalytic addition of ethyl nitroacetate 142 to cyclopent‐1...Scheme 6.43 Aminocatalytic conjugate additions of nitromethane to cyclopent‐...Scheme 6.44 Conversion of the γ‐nitroaldehyde 145 to the...Scheme 6.45 Conversion of the γ‐nitroaldehyde adduct 145 to the...Scheme 6.46 5‐(Trifluoromethyl)‐2‐isoxazoline veterinary drugs.Scheme 6.47 Nissan Chemical Industry approach to the 5‐(trifluoromethyl)‐2‐i...Scheme 6.48 Enantioselective preparation of 5‐(trifluoromethyl)‐2‐isoxazolin...Scheme 6.49 Proposed reaction pathway and transition‐state model A with a ci...Scheme 6.50 Application of the PTC 5‐(trifluoromethyl)‐2‐isoxazoline formati...Scheme 6.51 Application of the PTC isoxazoline forming reaction to azetidine...Scheme 6.52 Large‐scale examples of the utilization of catalyst 172 in (S)‐a...Scheme 6.53 PTC enantioselective reaction with Syngenta's candidates: select...Scheme 6.54 Dimeric quininium catalysts 186, 187 in the diastereoselective i...

7 Chapter 7Scheme 7.1 Biocatalytic strategies for chiral amine synthesis. Opine dehydro...Scheme 7.2 Evolution of the substrate scope of the monoamine oxidase from As...Scheme 7.3 Enzymatic cascades involving MAO‐N variants for the preparation o...Scheme 7.4 Chemoenzymatic cascades involving MAO‐N variants for the preparat...Scheme 7.5 CHAO variants in the biocatalytic deracemization of THQs.Scheme 7.6 6‐HDNO wild‐type (black) and D350L/E352D (blue) cyclic amine subs...Scheme 7.7 Difference between reactions catalyzed by AADH and AmDH.Scheme 7.8 Selected substrate scope of the original AmDH variants developed ...Scheme 7.9 Examples of preparative scale reactions using natural AmDH.Scheme 7.10 Longer chain ketones accepted by the pocket‐expanded AmDH descri...Scheme 7.11 Scale‐up reductive amination of 2‐phenoxypropanone. CFE, cell‐fr...Scheme 7.12 Preparative scale biosynthesis of benzylic amines.Scheme 7.13 AmDH synthesis of intermediate for ethambutol.Scheme 7.14 Biocatalytic hydrogen borrowing cascade for chiral amine synthes...Scheme 7.15 Sequential dihydroxylation/hydrogen borrowing amino‐hydroxylatio...Scheme 7.16 Imine reductases in biosynthesis.Scheme 7.17 Enantioselective reduction of 2‐methylpyrroline.Scheme 7.18 Further Mitsukura IRED transformations.Scheme 7.19 IREDs in biocatalytic cascade synthesis.Scheme 7.20 IREDs in chemoenzymatic synthesis.Scheme 7.21 IRED‐catalyzed reductive amination reactions.Scheme 7.22 Applications of reductive aminases in amine alkylation cascades....Scheme 7.23 Reductive aminase‐catalyzed step in the synthesis of GSK2879552....Scheme 7.24 P411‐catalyzed intramolecular C–H amination.Scheme 7.25 Applications of engineered cytochrome P411 biocatalysts for chir...

8 Chapter 8Figure 8.1 Overview of the various methods to identify and quantify amino gr...Figure 8.2 (a) Cycloaddition of azomethine ylides to C₆₀. (b) Arylation reac...Figure 8.3 (a) Reaction pathway for obtaining water‐soluble ammonium‐modifie...Figure 8.4 (a) Synthetic protocol for the MW‐induced double functionalizatio...Figure 8.5 (a) Functionalization of graphene via 1,3‐dipolar cycloaddition a...Figure 8.6 (a) Synthetic protocol for the production of water‐soluble amino ...Figure 8.7 Schematic illustration for the exfoliation of graphite through ba...Figure 8.8 Transmission electron micrographs of carbon nanohorns: (a) close‐...Figure 8.9 TEM images of triamide–NH conjugate in a series of bent conformat...Figure 8.10 TEM micrograph of 10 nm diameter nanodiamond.Figure 8.11 TEM images of carbon nano‐onions.Figure 8.12 Amino functionalization of CNO by (a) cycloaddition reaction on ...Figure 8.13 Role of amine precursors in the synthesis of CD. Depending on th...Figure 8.14 Examples of doping strategies to tailor the properties of NCDs d...Figure 8.15 Examples of nanoconjugates obtained from the coupling of functio...Figure 8.16 Schematic representations of 2D‐SAM, (a) amine head groups ancho...Figure 8.17 Schematic representation of the strategy described in Ref. [147]...Figure 8.18 Reaction pathways in sulfur–octylamine solution at 130 °C.Figure 8.19 Relative displacement potency labeled with the percentage of Lew...Figure 8.20 Representative TEM images for oleylamine‐based synthesis of gold...Figure 8.21 (a) TEM images of the concave Pt nanocrystals. (b) SEM image of ...Figure 8.22 Assembly steps for siRNA/PEI/PAH‐Cit/AuNP–CS complexes and pH‐re...

9 Chapter 9Figure 9.1 (a) Chitin and (b) cellulose structures.Figure 9.2 One‐pot synthesis of ADS from chitin.Figure 9.3 Conversion of NAG to AcGly catalyzed by Ru/C.Figure 9.4 Synthesis of ADI from ADS.Figure 9.5 Synthesis of 3A5AF from NAG.Figure 9.6 Direct conversion of chitin into 3A5AF.Figure 9.7 Structures of nitrogen compounds obtained from 3A5AF.Figure 9.8 Selective synthesis of deoxyfructosazine and fructosazine from D‐...Figure 9.9 Hydrogenation–decarbonylation of natural amino acids.Figure 9.10 Proposed mechanism for the metal‐free decarboxylation of amino a...Figure 9.11 Synthesis of primary amines by decarboxylation of amino acids....Figure 9.12 Synthesis of formamides by tandem decarboxylation–N‐formylation ...Figure 9.13 Reductive aminolysis of glucose into C2‐diamines.Figure 9.14 Synthesis of alkanolamines and ethylene diamines from glycolalde...Figure 9.15 Direct hydroxyethylation of amines by carbohydrates.Figure 9.16 Synthesis of HMMP from DHA.Figure 9.17 Proposed mechanism for the synthesis of HMMP.Figure 9.18 One‐pot synthesis of 2‐methyl pyrazine from glucose.Figure 9.19 One‐pot synthesis of furfurylamines from xylose.Figure 9.20 One‐pot synthesis of furfurylamines from xylose catalyzed by HRe...Figure 9.21 One‐pot conversion of xylan into furfurylamines.Figure 9.22 One‐pot synthesis of furfurylamines from xylan.Figure 9.23 Reductive amination of 5‐HMF catalyzed by Ru(DMP)₂Cl₂.Figure 9.24 Synthesis of BHMFA from 5‐HMF.Figure 9.25 Synthesis of BAMF from 5‐HMF.Figure 9.26 Synthesis of BAMF from DFF catalyzed by Rh/HZSM‐5.Figure 9.27 One‐pot conversion of xylose and xylan into α....Figure 9.28 One‐pot synthesis of α‐aminophosphonates from xylose and xylan....Figure 9.29 Synthesis of α‐aminophosphonates from 5‐HMF.Figure 9.30 Synthesis of 3,4‐dihydropyrimidin‐2‐ones from 5‐HMF.Figure 9.31 Synthesis of 2‐hydroxymethyl‐5‐methylpyrroles from 5‐HMF.Figure 9.32 Synthesis of pyrrolidinones and pyrrolidines from levulinic acid...Figure 9.33 Synthesis of a pyrrolidine from glucose catalyzed by an iridium ...Figure 9.34 Synthesis of pseudopeptides from levulinic acid.Figure 9.35 Synthesis of aminoketones, N‐formamides, and N‐methyl amines fro...Figure 9.36 Synthesis of alanine from glycerol.Figure 9.37 Proposed mechanism for the synthesis of alanine from glycerol....Figure 9.38 Synthesis of α‐amino acids from α‐hydroxy acids.Figure 9.39 Synthesis of aromatic N,N‐dimethyl tertiary amines from li...Figure 9.40 Synthesis 3,4‐dialkoxyanilines from 4‐propylguaiacol.Figure 9.41 Synthesis of 3,4‐dialkoxyanilines from 4‐propylguaiacol and 4‐pr...Figure 9.42 Synthesis of aminoalkylphenol derivatives and benzazepines from ...Figure 9.43 Catalytic amination of dihydroconiferyl and dihydrosinapyl alcoh...Figure 9.44 Synthesis of lignin‐derived tetrahydro‐2‐benzazepines in deep eu...Figure 9.45 N‐mono‐alkylation of aromatic and aliphatic amines with triglyce...Figure 9.46 Synthesis of fatty amines from triglycerides.Figure 9.47 Synthesis of fatty amides and nitriles from triglycerides.Figure 9.48 Synthesis of long‐chain diamines from long‐chain diols by direct...

10 Chapter 10Scheme 10.1 Historic strategies for the synthesis of aromatic amines.Scheme 10.2 Transition‐metal‐based methodologies for the preparation of arom...Scheme 10.3 (a) Ullmann's (1903) and (b) Goldberg's (1906) initial reports o...Scheme 10.4 Anticipated mechanism of the copper‐catalyzed C–N coupling react...Scheme 10.5 Examples of different conditions for the copper‐catalyzed C—N bo...Scheme 10.6 Examples of different modifications of the Ullmann C—N bond form...Scheme 10.7 Preparation of synthetic naphthalenoid H₃ antagonist 9 on a 14.5...Scheme 10.8 Synthesis of pyrazole 12 by large‐scale Ullmann coupling.Scheme 10.9 Preparation of annulated aniline derivative 14 as an intermediat...Scheme 10.10 Industrial‐scale synthesis of N‐cyclopropyl pyrazole derivative...Scheme 10.11 Migita's early report on a palladium‐catalyzed C–N coupling rea...Scheme 10.12 Buchwald's and Hartwig's initial reports of a palladium‐catalyz...Scheme 10.13 Mechanistic cycle of the palladium‐catalyzed C–N coupling react...Scheme 10.14 Evolution of the ligands for the Buchwald–Hartwig amination rea...Scheme 10.15 Preparation of N‐p‐tolyl‐substituted benzophenone hydrazine der...Scheme 10.16 Preparation of intermediate 23 for the synthesis of a 5‐HT rece...Scheme 10.17 C–N coupling of pyridazinium chloride 24 and amino pyrazole 25....Scheme 10.18 Regioselective and enantiospecific C–N coupling of isoquinoline...Scheme 10.19 Preparation of the precursor 32 for AMG 925 by Amgen.Scheme 10.20 Aromatic C—N bond formation approaches.Scheme 10.21 Palladium‐catalyzed aryl C–H amination.Scheme 10.22 Rhodium‐catalyzed direct C–H amination with aryl azides.Scheme 10.23 Synthetic versatility of diarylamine products from C–H aminatio...Scheme 10.24 Rhodium‐catalyzed C–H amination and synthetic utilities.Scheme 10.25 C–H amination enabled by a dirhodium catalyst.Scheme 10.26 Diarylamine synthesis via iridium‐nitrenoid catalyzed C–H amina...Scheme 10.27 Nickel‐catalyzed aryl C–H amination with alkyl amines.Scheme 10.28 Long‐standing challenge of using ammonia as an aminating agent ...Scheme 10.29 Nickel‐mediated C–H amination with ammonia.Scheme 10.30 Cobalt‐catalyzed aryl C–H amination and directing group hydroly...Scheme 10.31 Amination of benzylamine picolinamide.Scheme 10.32 Copper‐catalyzed C—N bond formation using dibenzothiophene sulf...Scheme 10.33 Copper‐catalyzed primary aniline synthesis.Scheme 10.34 Iron‐catalyzed C–H functionalization using ammonia surrogate 34Scheme 10.35 Organocatalyic C–H oxidative amination.Scheme 10.36 Typical modes of action of photocatalysis.Scheme 10.37 Synthesis of anilines enabled by a photoredox acridinium cataly...Scheme 10.38 Photoredox‐catalyzed C–H amination: substrate scope.Scheme 10.39 Reaction scope of ruthenium‐catalyzed C–H amination.Scheme 10.40 Synthesis of aniline derivatives via a sequence of C–H pyridina...Scheme 10.41 Photocatalytic amination of benzene with 37.Scheme 10.42 Aniline synthesis via electrochemical C–H amination.Scheme 10.43 Electrochemical C–H amination by cobalt catalysis. (a) Lei's sy...Scheme 10.44 Copper‐mediated decarboxylative amination of 38.Scheme 10.45 Palladium‐catalyzed decarboxylative couplings.Scheme 10.46 C–H amination under Pd/Cu dual catalysis.Scheme 10.47 Nickel‐catalyzed amination of aryl/heteroaryl chlorides.Scheme 10.48 Ni(NHC)‐catalyzed amination of aryl/heteroaryl chlorides.Scheme 10.49 Nickel‐catalyzed amination of aryl chlorides using silane reduc...Scheme 10.50 First example of room temperature nickel‐catalyzed amination of...Scheme 10.51 Nickel‐catalyzed amination of aryl/heteroaryl chlorides with pr...Scheme 10.52 Comparison of (a) Stradiotto's and (b) Hartwig's nickel‐catalyz...Scheme 10.53 Gram‐scale, nickel‐catalyzed amination of 2‐naphthyl bromide.Scheme 10.54 Nickel‐catalyzed amination of electrophilic coupling partners o...Scheme 10.55 C–F amination of N-PMB-protected paroxetine (top) and a liquid ...Scheme 10.56 Nickel‐catalyzed C–N couplings developed by Buchwald.Scheme 10.57 Nickel‐catalyzed amination of phenols via C–O activation.Scheme 10.58 Nickel‐catalyzed amination of aryl fluorosulfonates.Scheme 10.59 Cadmium‐catalyzed amination of iodobenzene.Scheme 10.60 Iron‐catalyzed amination of aryl halides.Scheme 10.61 Cobalt‐catalyzed amination of N‐aromatic‐2‐chlorides.Scheme 10.62 Rhodium‐catalyzed amination of bromobenzene derivatives.Scheme 10.63 Copper‐mediated amination of arylsilanes.Scheme 10.64 B(C₆F₅)₃–H₂O‐catalyzed reductive amination using silane reducta...Scheme 10.65 Palladium‐catalyzed reduction and reductive amination of nitroa...Scheme 10.66 Metal‐free reductive amination using hydrosilanes.Scheme 10.67 Gold‐catalyzed intermolecular hydroamination of allenes with ar...Scheme 10.68 Enantioselective rhodium‐catalyzed hydroamination of monosubsti...Scheme 10.69 Copper‐catalyzed hydroamination of phenylallene.Scheme 10.70 Enantioselective hydroamination of alkynes by Au(I)/...Scheme 10.71 Copper‐catalyzed asymmetric hydroamination.Scheme 10.72 Enantioselective copper‐catalyzed hydroamination of styrene wit...Scheme 10.73 Copper‐catalyzed anti‐Markovnikov hydroamination of vinylarenes...Scheme 10.74 Synthesis of indoline via Cu‐catalyzed hydroamination/Pd‐cataly...Scheme 10.75 Buchwald's flow synthesis of biarylamines and imatinib 46.Scheme 10.76 Meadows' continuous synthesis of arylamine 49 with bulky NHC pr...Scheme 10.77 Continuous‐flow S_NAr of heterocycles with nitrogen nucleophiles...Scheme 10.78 (a) Stepwise and (b) one‐pot synthesis with two C—N bond format...Scheme 10.79 Continuous synthesis of pyrazole 55 with a S_NAr reaction.Scheme 10.80 Continuous synthesis of cumidine via nitration and hydrogenatio...Scheme 10.81 Catalytic Chan–Lam reaction in continuous flow developed by Bax...Scheme 10.82 C–N coupling of secondary amine with supported SPhos.Scheme 10.83 Selected examples of supported NHC‐Pd catalysts.