Methodologies in Amine Synthesis

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 C 60. (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) 2Cl 2.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 H 3antagonist 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(C 6F 5) 3–H 2O‐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.