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Heterocyclic Chemistry at a Glance

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    1. Heterocyclic Nomenclature Introduction to Second Edition xiv



    • Six-membered aromatic heterocycles

    • Five-membered aromatic heterocycles

    • Non-aromatic heterocycles

    • Small-ring heterocycles





    1. Structures of Heteroaromatic Compounds



    • Structures of benzene and naphthalene

    • Structures of pyridines and pyridiniums

    • Structures of quinolines and isoquinolines

    • Structures of diazines (illustrated using pyrimidine)

    • Structures of pyrroles, thiophenes and furans

    • Structure of indoles

    • Structures of azoles (illustrated using imidazole)





    1. Common Reaction Types in Heterocyclic Chemistry



    • Introduction

    • Acidity and basicity

    • Electrophilic substitution of aromatic molecules

    • Nucleophilic substitution of aromatic molecules

    • Radical substitution of heterocycles

    • C-Metallated heterocycles as nucleophiles

    • Generation of C-metallated heterocycles

    • Dimethylformamide dimethyl acetal (DMFDMA)

    • Formation and hydrolysis of imine/enamine

    • Common synthetic equivalents of carbonyl compounds in ring synthesis

    • Cycloaddition reactions





    1. Palladium in Heterocyclic Chemistry



    • Palladium(0)-catalysed (and related) reactions

    • Addition to alkenes: the Heck reaction

    • Carbonylation reactions

    • halides – making carbon–heteroatom bonds Cross-coupling reactions between heteroatom nucleophiles and

    • Tr i fl ates as substrates for palladium-catalysed reactions

    • Mechanisms of palladium(0)-catalysed processes

    • Reactions involving electrophilic palladation

    • Copper-catalysed amination

    • Selectivity





    1. Pyridines Contents vii



    • Electrophilic addition to nitrogen

    • Electrophilic substitution at carbon

    • Nucleophilic substitution

    • Nucleophilic addition to pyridinium salts

    • C-metallated pyridines

    • Palladium(0)-catalysed reactions

    • Oxidation and reduction

    • Pericyclic reactions

    • Alkyl and carboxylic acid substituents

    • Oxygen substituents

    • N-Oxides

    • Amine substituents

    • Ring synthesis – disconnections

    • Synthesis of pyridines from 1,5-dicarbonyl compounds

    • Synthesis of pyridines from an aldehyde, two equivalents of a 1,3-dicarbonyl compound and ammonia

    • Synthesis of pyridines from 1,3-dicarbonyl compounds and a C 2 N unit

    • Exercises





    1. Diazines



    • Electrophilic addition to nitrogen

    • Electrophilic substitution at carbon

    • Nucleophilic substitution

    • Radical substitution

    • C-Metallated diazines

    • Palladium(0)-catalysed reactions

    • Pericyclic reactions

    • Oxygen substituents

    • N-Oxides

    • Amine substituents

    • Ring synthesis – disconnections

    • Synthesis of pyridazines from 1,4-dicarbonyl compounds

    • Synthesis of pyrimidines from 1,3-dicarbonyl compounds

    • Synthesis of pyrazines from 1,2-dicarbonyl compounds

    • Synthesis of pyrazines from -amino-carbonyl compounds

    • Benzodiazines

    • Exercises





    1. Quinolines and Isoquinolines



    • Electrophilic addition to nitrogen

    • Electrophilic substitution at carbon

    • Nucleophilic substitution

    • Nucleophilic addition to quinolinium/isoquinolinium salts

    • C-Metallated quinolines and isoquinolines

    • Palladium(0)-catalysed reactions

    • Oxidation and reduction

    • Alkyl substituents

    • Oxygen substituents

    • N-Oxides

    • Ring synthesis – disconnections

    • Synthesis of quinolines from anilines

    • Synthesis of quinolines from ortho-aminoaryl ketones or aldehydes

    • Synthesis of isoquinolines from 2-arylethamines

    • Synthesis of isoquinolines from aryl-aldehydes and an aminoacetaldehyde acetal viii Contents

    • Synthesis of isoquinolines from ortho-alkynyl aryl-aldehydes or corresponding imines

    • Exercises





    1. Pyryliums, Benzopyryliums, Pyrones and Benzopyrones



    • Pyrylium salts

    • Electrophiles

    • Nucleophilic addition

    • Ring-opening reactions of 2H-pyrans

    • Oxygen substituents – pyrones and benzopyrones

    • Ring synthesis of pyryliums from 1,5-diketones

    • Ring synthesis of 4-pyrones from 1,3,5-triketones

    • Ring synthesis of 2-pyrones from 1,3-keto-aldehydes

    • Ring synthesis of 1-benzopyryliums, coumarins and chromones

    • Exercises





    1. Pyrroles



    • Electrophilic substitution at carbon

    • N-Deprotonation and N-metallated pyrroles

    • C-Metallated pyrroles

    • Palladium(0)-catalysed reactions

    • Oxidation and reduction

    • Pericyclic reactions

    • Reactivity of side-chain substituents

    • The ‘pigments of life’

    • Ring synthesis – disconnections

    • Synthesis of pyrroles from 1,4-dicarbonyl compounds

    • Synthesis of pyrroles from -amino-ketones

    • Synthesis of pyrroles using isocyanides

    • Exercises





    1. Indoles



    • Electrophilic substitution at carbon

    • N-Deprotonation and N-metallated indoles

    • C-Metallated indoles

    • Palladium(0)-catalysed reactions

    • Oxidation and reduction

    • Pericyclic reactions

    • Reactivity of side-chain substituents

    • Oxygen substituents

    • Ring synthesis – disconnections

    • Synthesis of indoles from arylhydrazones

    • Synthesis of indoles from ortho-nitrotoluenes

    • Synthesis of indoles from ortho-aminoaryl alkynes

    • Synthesis of indoles from ortho-alkylaryl isocyanides

    • Synthesis of indoles from ortho-acyl anilides

    • Synthesis of isatins from anilines

    • Synthesis of oxindoles from anilines

    • Synthesis of indoxyls from anthranilic acids

    • Azaindoles

    • Exercises





    1. Furans and Thiophenes



    • Electrophilic substitution at carbon

    • C-Metallated thiophenes and furans

    • Palladium(0)-catalysed reactions Contents ix

    • Oxidation and reduction

    • Pericyclic reactions

    • Oxygen substituents

    • Ring synthesis – disconnections

    • Synthesis of furans and thiophenes from 1,4-dicarbonyl compounds

    • Exercises





    1. 1,2-Azoles and 1,3-Azoles



    • Introduction

    • Electrophilic addition to N

    • Electrophilic substitution at C

    • Nucleophilic substitution of halogen

    • N-Deprotonation and N-metallated imidazoles and pyrazoles

    • thiazoles and isothiazoles C-Metallated N-substituted imidazoles and pyrazoles, and C-metallated

    • C-Deprotonation of oxazoles and isoxazoles

    • Palladium(0)-catalysed reactions

    • 1,3-Azolium ylides

    • Reductions

    • Pericyclic reactions

    • Oxygen and amine substituents

    • 1,3-Azoles ring synthesis – disconnections

    • Synthesis of thiazoles and imidazoles from -halo-ketones

    • Synthesis of 1,3-azoles from 1,4-dicarbonyl compounds

    • Synthesis of 1,3-azoles using tosylmethyl isocyanide

    • Synthesis of 1,3-azoles via dehydrogenation

    • 1,2-Azoles ring synthesis – disconnections

    • Synthesis of pyrazoles and isoxazoles from 1,3-dicarbonyl compounds

    • Synthesis of isoxazoles and pyrazoles from alkynes

    • Synthesis of isothiazoles from -amino , -unsaturated carbonyl compounds

    • Exercises





    1. Purines



    • Electrophilic addition to nitrogen

    • Electrophilic substitution at carbon

    • N-Deprotonation and N-metallated purines

    • Oxidation

    • Nucleophilic substitution

    • C-Metallated purines by direct deprotonation or halogen–metal exchange

    • Palladium(0)-catalysed reactions

    • Purines with oxygen and amine substituents

    • Ring synthesis – disconnections

    • Synthesis of purines from 4,5-diaminopyrimidines

    • Synthesis of purines from 5-aminoimidazole-4-carboxamide

    • ‘One-step syntheses’

    • Exercises

    • and Higher Azines (6-Membered) 14. Heterocycles with More than Two Heteroatoms: Higher Azoles (5-Membered)

    • Higher Azoles

    • Introduction

    • tetrazole and pentazole Higher azoles containing nitrogen as the only ring heteroatom: triazoles,

    • Benzotriazole x Contents

    • Higher azoles also containing ring sulfur or oxygen: oxa- and thiadiazoles

    • Higher azines

    • Exercises





    1. Heterocycles with Ring-Junction Nitrogen (Bridgehead Nitrogen)



    • Introduction

    • Indolizine

    • Azaindolizines

    • Synthesis of indolizines and azaindolizines

    • Quinoliziniums and quinolizinones

    • Heteropyrrolizines (pyrrolizines containing additional heteroatoms)

    • Cyclazines

    • Exercises





    1. Non-Aromatic Heterocycles



    • Introduction

    • Three-membered rings

    • Four-membered rings

    • Five- and six-membered rings

    • Ring synthesis





    1. Heterocycles in Nature



    • Heterocyclic -amino acids and related substances

    • Heterocyclic vitamins – co-enzymes

    • Porphobilinogen and the ‘Pigments of Life’

    • and ribonucleic acid (RNA), its deliverer Deoxyribonucleic acid (DNA), the store of genetic information,

    • Heterocyclic secondary metabolites





    1. Heterocycles in Medicine



    • Medicinal chemistry – how drugs function

    • Drug discovery

    • Drug development

    • The neurotransmitters

    • Histamine

    • Acetylcholine (ACh)

    • Anticholinesterase agents

    • 5-Hydroxytryptamine (5-HT) (serotonin)

    • Adrenaline and noradrenaline

    • Other signifi cant cardiovascular drugs

    • Drugs acting specifi cally on the CNS

    • Other enzyme inhibitors

    • Anti-infective agents

    • Antiparasitic drugs

    • Antibacterial drugs

    • Antiviral drugs

    • Anticancer drugs

    • Photochemotherapy





    1. Applications and Occurrences of Heterocycles in Everyday Life



    • Introduction

    • Dyes and pigments

    • Polymers Contents xi

    • Pesticides

    • Explosives

    • Food and drink

    • Heterocyclic chemistry of cooking

    • Natural and synthetic food colours

    • Flavours and fragrances (F&F)

    • Toxins

    • Electrical and electronic



  • Index

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