Methodologies in Amine Synthesis

2 Chapter 2 Scheme 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(sp 3)–H imination of tertiary aliph... Scheme 2.5 Photoinduced aminosulfonylation of C(sp 3)—H bonds with sulfur dio... Scheme 2.6 Redox neutral remote functionalization of C(sp 3)—H bonds via imin... Scheme 2.7 Intermolecular remote C(sp 3)–H and C–C vinylations via iminyl rad... Scheme 2.8 Remote C(sp 3)–H allyation of amides using organic photocatalyst.... Scheme 2.9 Site‐selective remote C(sp 3)–H heteroarylation of amides. Scheme 2.10 Visible‐light‐promoted C(sp 3)–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(sp 3)—H bonds.... Scheme 2.14 Remote amide allylation using allyl chlorides and Ni(0) cocataly... Scheme 2.15 Regioselective cross‐coupling of C(sp 3)—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(sp 3)–H chlorination and... Scheme 2.21 Iron‐catalyzed remote C(sp 3)–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(sp 3)—H bonds via amidyl r... Scheme 2.24 Enantioselective remote C–H cyanation of amines via copper‐catal...

3 Chapter 3 Scheme 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 H 2lib... Scheme 3.34 Visible‐light‐enabled direct benzylic C(sp 3)–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(sp 3)–H/N–H cross‐coup...

4 Chapter 4 Figure 4.1 Propargylamines: synthetic methods and drugs containing a proparg...Scheme 4.1 Chiral ligands used in asymmetric A 3coupling reactions.Scheme 4.2 Li's approach to the enantioselective synthesis of propargylamine...Scheme 4.3 Enantioselective A 3coupling approaches to propargylamines.Scheme 4.4 Knochel's enantioselective synthesis of propargylamines.Scheme 4.5 Proposed mechanism for the ( R )‐(+)‐Quinap‐catalyzed A 3coupling....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 A 3coupling 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 CS 2.Scheme 4.54 Reactions of propargylamine with isothiocyanates.Scheme 4.55 Synthesis of thiazoline derivatives from N ‐propargylamines using...