Efnisyfirlit

• Cover
• Title page
• Copyright page
• Brief contents
• Contents
• Abbreviations
• Preface to the second edition
• Organic chemistry and this book
• 1 What is organic chemistry?
  • Organic chemistry and you
  • Organic compounds
  • Organic chemistry and industry
  • Organic chemistry and the periodic table
  • Organic chemistry and this book
  • Further reading
• 2 Organic structures
  • Hydrocarbon frameworks and functional groups
  • Drawing molecules
  • Hydrocarbon frameworks
  • Functional groups
  • Carbon atoms carrying functional groups can be classified by oxidation level
  • Naming compounds
  • What do chemists really call compounds?
  • How should you name compounds?
  • Further reading
• 3 Determining organic structures
  • Introduction
  • Mass spectrometry
  • Mass spectrometry detects isotopes
  • Atomic composition can be determined by high-resolution mass spectrometry
  • Nuclear magnetic resonance
  • Regions of the 13C NMR spectrum
  • Different ways of describing chemical shift
  • A guided tour of the 13C NMR spectra of some simple molecules
  • The 1H NMR spectrum
  • Infrared spectra
  • Mass spectra, NMR, and IR combined make quick identification possible
  • Double bond equivalents help in the search for a structure
  • Looking forward to Chapters 13 and 18
  • Further reading
• 4 Structure of molecules
  • Introduction
  • Electrons occupy atomic orbitals
  • Molecular orbitals—diatomic molecules
  • Bonds between different atoms
  • Hybridization of atomic orbitals
  • Rotation and rigidity
  • Conclusion
  • Looking forward
  • Further reading
• 5 Organic reactions
  • Chemical reactions
  • Nucleophiles and electrophiles
  • Curly arrows represent reaction mechanisms
  • Drawing your own mechanisms with curly arrows
  • Further reading
• 6 Nucleophilic addition to the carbonyl group
  • Molecular orbitals explain the reactivity of the carbonyl group
  • Attack of cyanide on aldehydes and ketones
  • The angle of nucleophilic attack on aldehydes and ketones
  • Nucleophilic attack by ‘hydride’ on aldehydes and ketones
  • Addition of organometallic reagents to aldehydes and ketones
  • Addition of water to aldehydes and ketones
  • Hemiacetals from reaction of alcohols with aldehydes and ketones
  • Ketones also form hemiacetals
  • Acid and base catalysis of hemiacetal and hydrate formation
  • Bisulfite addition compounds
  • Further reading
• 7 Delocalization and conjugation
  • Introduction
  • The structure of ethene (ethylene, CH2=CH2)
  • Molecules with more than one C=C double bond
  • The conjugation of two π bonds
  • UV and visible spectra
  • The allyl system
  • Delocalization over three atoms is a common structural feature
  • Aromaticity
  • Further reading
• 8 Acidity, basicity, and pKa
  • Organic compounds are more soluble in water as ions
  • Acids, bases, and pKa
  • Acidity
  • The definition of pKa
  • Constructing a pKa scale
  • Nitrogen compounds as acids and bases
  • Substituents affect the pKa
  • Carbon acids
  • pKa in action—the development of the drug cimetidine
  • Lewis acids and bases
  • Further reading
• 9 Using organometallic reagents to make C–C bonds
  • Introduction
  • Organometallic compounds contain a carbon–metal bond
  • Making organometallics
  • Using organometallics to make organic molecules
  • Oxidation of alcohols
  • Looking forward
  • Further reading
• 10 Nucleophilic substitution at the carbonyl group
  • The product of nucleophilic addition to a carbonyl group is not always a stable compound
  • Carboxylic acid derivatives
  • Why are the tetrahedral intermediates unstable?
  • Not all carboxylic acid derivatives are equally reactive
  • Acid catalysts increase the reactivity of a carbonyl group
  • Acid chlorides can be made from carboxylic acids using SOCl2 or PCl5
  • Making other compounds by substitution reactions of acid derivatives
  • Making ketones from esters: the problem
  • Making ketones from esters: the solution
  • To summarize…
  • And to conclude…
  • Further reading
• 11 Nucleophilic substitution at C=O with loss of carbonyl oxygen
  • Introduction
  • Aldehydes can react with alcohols to form hemiacetals
  • Acetals are formed from aldehydes or ketones plus alcohols in the presence of acid
  • Amines react with carbonyl compounds
  • Imines are the nitrogen analogues of carbonyl compounds
  • Summary
  • Further reading
• 12 Equilibria, rates, and mechanisms
  • How far and how fast?
  • How to make the equilibrium favour the product you want
  • Entropy is important in determining equilibrium constants
  • Equilibrium constants vary with temperature
  • Introducing kinetics: how to make reactions go faster and cleaner
  • Rate equations
  • Catalysis in carbonyl substitution reactions
  • Kinetic versus thermodynamic products
  • Summary of mechanisms from Chapters 6–12
  • Further reading
• 13 1H NMR: Proton nuclear magnetic resonance
  • The differences between carbon and proton NMR
  • Integration tells us the number of hydrogen atoms in each peak
  • Regions of the proton NMR spectrum
  • Protons on saturated carbon atoms
  • The alkene region and the benzene region
  • The aldehyde region: unsaturated carbon bonded to oxygen
  • Protons on heteroatoms have more variable shifts than protons on carbon
  • Coupling in the proton NMR spectrum
  • To conclude
  • Further reading
• 14 Stereochemistry
  • Some compounds can exist as a pair of mirror-image forms
  • Diastereoisomers are stereoisomers that are not enantiomers
  • Chiral compounds with no stereogenic centres
  • Axes and centres of symmetry
  • Separating enantiomers is called resolution
  • Further reading
• 15 Nucleophilic substitution at saturated carbon
  • Mechanisms for nucleophilic substitution
  • How can we decide which mechanism (SN1 or SN2) will apply to a given organic compound?
  • A closer look at the SN1 reaction
  • A closer look at the SN2 reaction
  • Contrasts between SN1 and SN2
  • The leaving group in SN1 and SN2 reactions
  • The nucleophile in SN1 reactions
  • The nucleophile in the SN2 reaction
  • Nucleophiles and leaving groups compared
  • Looking forward: elimination and rearrangement reactions
  • Further reading
• 16 Conformational analysis
  • Bond rotation allows chains of atoms to adopt a number of conformations
  • Conformation and configuration
  • Barriers to rotation
  • Conformations of ethane
  • Conformations of propane
  • Conformations of butane
  • Ring strain
  • A closer look at cyclohexane
  • Substituted cyclohexanes
  • To conclude…
  • Further reading
• 17 Elimination reactions
  • Substitution and elimination
  • How the nucleophile affects elimination versus substitution
  • E1 and E2 mechanisms
  • Substrate structure may allow E1
  • The role of the leaving group
  • E1 reactions can be stereoselective
  • E2 eliminations have anti-periplanar transition states
  • The regioselectivity of E2 eliminations
  • Anion-stabilizing groups allow another mechanism—E1cB
  • To conclude
  • Further reading
• 18 Review of spectroscopic methods
  • There are three reasons for this chapter
  • Spectroscopy and carbonyl chemistry
  • Acid derivatives are best distinguished by infrared
  • Small rings introduce strain inside the ring and higher s character outside it
  • Simple calculations of C=O stretching frequencies in IR spectra
  • NMR spectra of alkynes and small rings
  • Proton NMR distinguishes axial and equatorial protons in cyclohexanes
  • Interactions between different nuclei can give enormous coupling constants
  • Identifying products spectroscopically
  • Tables
  • Shifts in proton NMR are easier to calculate and more informative than those in carbon NMR
  • Further reading
• 19 Electrophilic addition to alkenes
  • Alkenes react with bromine
  • Oxidation of alkenes to form epoxides
  • Electrophilic addition to unsymmetrical alkenes is regioselective
  • Electrophilic addition to dienes
  • Unsymmetrical bromonium ions open regioselectively
  • Electrophilic additions to alkenes can be stereospecific
  • Adding two hydroxyl groups: dihydroxylation
  • Breaking a double bond completely: periodate cleavage and ozonolysis
  • Adding one hydroxyl group: how to add water across a double bond
  • To conclude…a synopsis of electrophilic addition reactions
  • Further reading
• 20 Formation and reactions of enols and enolates
  • Would you accept a mixture of compounds as a pure substance?
  • Tautomerism: formation of enols by proton transfer
  • Why don’t simple aldehydes and ketones exist as enols?
  • Evidence for the equilibration of carbonyl compounds with enols
  • Enolization is catalysed by acids and bases
  • The intermediate in the base-catalysed reaction is an enolate ion
  • Summary of types of enol and enolate
  • Stable enols
  • Consequences of enolization
  • Reaction with enols or enolates as intermediates
  • Stable equivalents of enolate ions
  • Enol and enolate reactions at oxygen: preparation of enol ethers
  • Reactions of enol ethers
  • To conclude
  • Further reading
• 21 Electrophilic aromatic substitution
  • Introduction: enols and phenols
  • Benzene and its reactions with electrophiles
  • Electrophilic substitution on phenols
  • A nitrogen lone pair activates even more strongly
  • Alkyl benzenes also react at the ortho and para positions
  • Electron-withdrawing substituents give meta products
  • Halogens show evidence of both electron withdrawal and donation
  • Two or more substituents may cooperate or compete
  • Some problems and some opportunities
  • A closer look at Friedel–Crafts chemistry
  • Exploiting the chemistry of the nitro group
  • Summary
  • Further reading
• 22 Conjugate addition and nucleophilic aromatic substitution
  • Alkenes conjugated with carbonyl groups
  • Conjugated alkenes can be electrophilic
  • Summary: factors controlling conjugate addition
  • Extending the reaction to other electron-deficient alkenes
  • Conjugate substitution reactions
  • Nucleophilic epoxidation
  • Nucleophilic aromatic substitution
  • The addition–elimination mechanism
  • The SN1 mechanism for nucleophilic aromatic substitution: diazonium compounds
  • The benzyne mechanism
  • To conclude…
  • Further reading
• 23 Chemoselectivity and protecting groups
  • Selectivity
  • Reducing agents
  • Reduction of carbonyl groups
  • Hydrogen as a reducing agent: catalytic hydrogenation
  • Getting rid of functional groups
  • Dissolving metal reductions
  • Selectivity in oxidation reactions
  • Competing reactivity: choosing which group reacts
  • A survey of protecting groups
  • Further reading
• 24 Regioselectivity
  • Introduction
  • Regioselectivity in electrophilic aromatic substitution
  • Electrophilic attack on alkenes
  • Regioselectivity in radical reactions
  • Nucleophilic attack on allylic compounds
  • Electrophilic attack on conjugated dienes
  • Conjugate addition
  • Regioselectivity in action
  • Further reading
• 25 Alkylation of enolates
  • Carbonyl groups show diverse reactivity
  • Some important considerations that affect all alkylations
  • Nitriles and nitroalkanes can be alkylated
  • Choice of electrophile for alkylation
  • Lithium enolates of carbonyl compounds
  • Alkylations of lithium enolates
  • Using specific enol equivalents to alkylate aldehydes and ketones
  • Alkylation of β-dicarbonyl compounds
  • Ketone alkylation poses a problem in regioselectivity
  • Enones provide a solution to regioselectivity problems
  • Using Michael acceptors as electrophiles
  • To conclude…
  • Further reading
• 26 Reactions of enolates with carbonyl compounds: the aldol and Claisen reactions
  • Introduction
  • The aldol reaction
  • Cross-condensations
  • Specific enol equivalents can be used to control aldol reactions
  • How to control aldol reactions of esters
  • How to control aldol reactions of aldehydes
  • How to control aldol reactions of ketones
  • Intramolecular aldol reactions
  • Acylation at carbon
  • Crossed ester condensations
  • Summary of the preparation of keto-esters by the Claisen reaction
  • Controlling acylation with specific enol equivalents
  • Intramolecular crossed Claisen ester condensations
  • Carbonyl chemistry—where next?
  • Further reading
• 27 Sulfur, silicon, and phosphorus in organic chemistry
  • Useful main group elements
  • Sulfur: an element of contradictions
  • Sulfur-stabilized anions
  • Sulfonium salts
  • Sulfonium ylids
  • Silicon and carbon compared
  • Allyl silanes as nucleophiles
  • The selective synthesis of alkenes
  • The properties of alkenes depend on their geometry
  • Exploiting cyclic compounds
  • Equilibration of alkenes
  • E and Z alkenes can be made by stereoselective addition to alkynes
  • Predominantly E alkenes can be formed by stereoselective elimination reactions
  • The Julia olefination is regiospecific and connective
  • Stereospecific eliminations can give pure single isomers of alkenes
  • Perhaps the most important way of making alkenes—the Wittig reaction
  • To conclude
  • Further reading
• 28 Retrosynthetic analysis
  • Creative chemistry
  • Retrosynthetic analysis: synthesis backwards
  • Disconnections must correspond to known, reliable reactions
  • Synthons are idealized reagents
  • Multiple step syntheses: avoid chemoselectivity problems
  • Functional group interconversion
  • Two-group disconnections are better than one-group disconnections
  • C–C disconnections
  • Available starting materials
  • Donor and acceptor synthons
  • Two-group C–C disconnections
  • 1,5-Related functional groups
  • ‘Natural reactivity’ and ‘umpolung’
  • To conclude…
  • Further reading
• 29 Aromatic heterocycles 1: reactions
  • Introduction
  • Aromaticity survives when parts of benzene’s ring are replaced by nitrogen atoms
  • Pyridine is a very unreactive aromatic imine
  • Six-membered aromatic heterocycles can have oxygen in the ring
  • Five-membered aromatic heterocycles are good at electrophilic substitution
  • Furan and thiophene are oxygen and sulfur analogues of pyrrole
  • More reactions of five-membered heterocycles
  • Five-membered rings with two or more nitrogen atoms
  • Benzo-fused heterocycles
  • Putting more nitrogen atoms in a six-membered ring
  • Fusing rings to pyridines: quinolines and isoquinolines
  • Aromatic heterocycles can have many nitrogens but only one sulfur or oxygen in any ring
  • There are thousands more heterocycles out there
  • Which heterocyclic structures should you learn?
  • Further reading
• 30 Aromatic heterocycles 2: synthesis
  • Thermodynamics is on our side
  • Disconnect the carbon–heteroatom bonds first
  • Pyrroles, thiophenes, and furans from 1,4-dicarbonyl compounds
  • How to make pyridines: the Hantzsch pyridine synthesis
  • Pyrazoles and pyridazines from hydrazine and dicarbonyl compounds
  • Pyrimidines can be made from 1,3-dicarbonyl compounds and amidines
  • Unsymmetrical nucleophiles lead to selectivity questions
  • Isoxazoles are made from hydroxylamine or by cycloaddition
  • Tetrazoles and triazoles are also made by cycloadditions
  • The Fischer indole synthesis
  • Quinolines and isoquinolines
  • More heteroatoms in fused rings mean more choice in synthesis
  • Summary: the three major approaches to the synthesis of aromatic heterocycles
  • Further reading
• 31 Saturated heterocycles and stereoelectronics
  • Introduction
  • Reactions of saturated heterocycles
  • Conformation of saturated heterocycles
  • Making heterocycles: ring-closing reactions
  • Ring size and NMR
  • Geminal (2J ) coupling
  • Diastereotopic groups
  • To summarize…
  • Further reading
• 32 Stereoselectivity in cyclic molecules
  • Introduction
  • Stereochemical control in six-membered rings
  • Reactions on small rings
  • Regiochemical control in cyclohexene epoxides
  • Stereoselectivity in bicyclic compounds
  • Fused bicyclic compounds
  • Spirocyclic compounds
  • Reactions with cyclic intermediates or cyclic transition states
  • To summarize…
  • Further reading
• 33 Diastereoselectivity
  • Looking back
  • Prochirality
  • Additions to carbonyl groups can be diastereoselective even without rings
  • Stereoselective reactions of acyclic alkenes
  • Aldol reactions can be stereoselective
  • Single enantiomers from diastereoselective reactions
  • Looking forward
  • Further reading
• 34 Pericyclic reactions 1: cycloadditions
  • A new sort of reaction
  • General description of the Diels–Alder reaction
  • The frontier orbital description of cycloadditions
  • Regioselectivity in Diels–Alder reactions
  • The Woodward–Hoffmann description of the Diels–Alder reaction
  • Trapping reactive intermediates by cycloadditions
  • Other thermal cycloadditions
  • Photochemical [2 + 2] cycloadditions
  • Thermal [2 + 2] cycloadditions
  • Making five-membered rings: 1,3-dipolar cycloadditions
  • Two very important synthetic reactions: cycloaddition of alkenes with osmium tetroxide and with ozone
  • Summary of cycloaddition reactions
  • Further reading
• 35 Pericyclic reactions 2: sigmatropic and electrocyclic reactions
  • Sigmatropic rearrangements
  • Orbital descriptions of [3,3]-sigmatropic rearrangements
  • The direction of [3,3]-sigmatropic rearrangements
  • [2,3]-Sigmatropic rearrangements
  • [1,5]-Sigmatropic hydrogen shifts
  • Electrocyclic reactions
  • Further reading
• 36 Participation, rearrangement, and fragmentation
  • Neighbouring groups can accelerate substitution reactions
  • Rearrangements occur when a participating group ends up bonded to a different atom
  • Carbocations readily rearrange
  • The pinacol rearrangement
  • The dienone-phenol rearrangement
  • The benzilic acid rearrangement
  • The Favorskii rearrangement
  • Migration to oxygen: the Baeyer–Villiger reaction
  • The Beckmann rearrangement
  • Polarization of C–C bonds helps fragmentation
  • Fragmentations are controlled by stereochemistry
  • Ring expansion by fragmentation
  • Controlling double bonds using fragmentation
  • The synthesis of nootkatone: fragmentation showcase
  • Looking forward
  • Further reading
• 37 Radical reactions
  • Radicals contain unpaired electrons
  • Radicals form by homolysis of weak bonds
  • Most radicals are extremely reactive…
  • How to analyse the structure of radicals: electron spin resonance
  • Radical stability
  • How do radicals react?
  • Radical–radical reactions
  • Radical chain reactions
  • Chlorination of alkanes
  • Allylic bromination
  • Reversing the selectivity: radical substitution of Br by H
  • Carbon–carbon bond formation with radicals
  • The reactivity pattern of radicals is quite different from that of polar reagents
  • Alkyl radicals from boranes and oxygen
  • Intramolecular radical reactions are more efficient than intermolecular ones
  • Looking forward
  • Further reading
• 38 Synthesis and reactions of carbenes
  • Diazomethane makes methyl esters from carboxylic acids
  • Photolysis of diazomethane produces a carbene
  • How do we know that carbenes exist?
  • Ways to make carbenes
  • Carbenes can be divided into two types
  • How do carbenes react?
  • Carbenes react with alkenes to give cyclopropanes
  • Insertion into C–H bonds
  • Rearrangement reactions
  • Nitrenes are the nitrogen analogues of carbenes
  • Alkene metathesis
  • Summary
  • Further reading
• 39 Determining reaction mechanisms
  • There are mechanisms and there are mechanisms
  • Determining reaction mechanisms: the Cannizzaro reaction
  • Be sure of the structure of the product
  • Systematic structural variation
  • The Hammett relationship
  • Other kinetic evidence for reaction mechanisms
  • Acid and base catalysis
  • The detection of intermediates
  • Stereochemistry and mechanism
  • Summary of methods for the investigation of mechanism
  • Further reading
• 40 Organometallic chemistry
  • Transition metals extend the range of organic reactions
  • The 18 electron rule
  • Bonding and reactions in transition metal complexes
  • Palladium is the most widely used metal in homogeneous catalysis
  • The Heck reaction couples together an organic halide or triflate and an alkene
  • Cross-coupling of organometallics and halides
  • Allylic electrophiles are activated by palladium(0)
  • Palladium-catalysed amination of aromatic rings
  • Alkenes coordinated to palladium(II) are attacked by nucleophiles
  • Palladium catalysis in the total synthesis of a natural alkaloid
  • An overview of some other transition metals
  • Further reading
• 41 Asymmetric synthesis
  • Nature is asymmetric
  • The chiral pool: Nature’s chiral centres ‘off the shelf’
  • Resolution can be used to separate enantiomers
  • Chiral auxiliaries
  • Chiral reagents
  • Asymmetric catalysis
  • Asymmetric formation of carbon–carbon bonds
  • Asymmetric aldol reactions
  • Enzymes as catalysts
  • Further reading
• 42 Organic chemistry of life
  • Primary metabolism
  • Life begins with nucleic acids
  • Proteins are made of amino acids
  • Sugars—just energy sources?
  • Lipids
  • Mechanisms in biological chemistry
  • Natural products
  • Fatty acids and other polyketides are made from acetyl CoA
  • Terpenes are volatile constituents of plants
  • Further reading
• 43 Organic chemistry today
  • Science advances through interaction between disciplines
  • Chemistry vs viruses
  • The future of organic chemistry
  • Further reading
• Figure acknowledgements
• Periodic table of the elements
• Index

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