Organic chemistry / Jonathan Clayden, Nick Greeves, Stuart Warren.

Format:

Book

Author/Creator:

Clayden, Jonathan.

Contributor:

Greeves, Nick.

Warren, Stuart G.

Language:

English

Subjects (All):

Chemistry, Organic--Textbooks.

Chemistry, Organic.

Genre:

Textbooks.

Lehrbuch.

Physical Description:

xxv, 1234 pages : illustrations (some color) ; 28 cm

Edition:

Second edition.

Place of Publication:

Oxford ; New YorK : Oxford University Press, [2012]

Summary:

A first- and second-year undergraduate organic chemistry textbook, specifically geared to British and European courses and those offered in better schools in North America, this text emphasises throughout clarity and understanding.

Inspiring and motivating students from the moment it published, Organic Chemistry has established itself in just one edition as the student's choice of an organic chemistry text. The second edition refines and refocuses Organic Chemistry to produce a text that is even more student-friendly, coherent, and logical in its presentation than before. Like the first, the second edition is built on three principles: An explanatory approach, through which the reader is motivated to understand the subject and not just learn the facts; A mechanistic approach, giving the reader the power to understand compounds and reactions never previously encountered; An evidence-based approach, setting out clearly how and why reactions happen as they do, giving extra depth to the reader's understanding. The authors write clearly and directly, sharing with the reader their own fascination with the subject, and leading them carefully from topic to topic. Their honest and open narrative flags pitfalls and misconceptions, guiding the reader towards a complete picture of organic chemistry and its universal themes and principles. -- From publisher's description.

Contents:

Note continued: 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(O)

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

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

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

43. Organic chemistry today

Science advances through interaction between disciplines

Chemistry vs viruses

The future of organic chemistry

Further reading.

Contents note continued: 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

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

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

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

26. Reactions of enolates with carbonyl compounds: the aldol and Claisen reactions

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

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

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'

29. Aromatic heterocycles 1: reactions

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

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

31. Saturated heterocycles and stereoelectronics

Reactions of saturated heterocycles

Conformation of saturated heterocycles

Making heterocycles: ring-closing reactions

Ring size and NMR

Geminal (2f) coupling

Diastereotopic groups

To summarize

32. Stereoselectivity in cyclic molecules

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

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

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

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

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

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

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

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

Machine generated contents note: 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

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

3. Determining organic structures

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

4. Structure of molecules

Electrons occupy atomic orbitals

Molecular orbitals

-diatomic molecules

Bonds between different atoms

Hybridization of atomic orbitals

Rotation and rigidity

Conclusion

5. Organic reactions

Chemical reactions

Nucleophiles and electrophiles

Curly arrows represent reaction mechanisms

Drawing your own mechanisms with curly arrows

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 nuceophilic 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

7. Delocalization and conjugation

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

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

9. Using organometallic reagents to make C-C bonds

Organometallic compounds contain a carbon-metal bond

Making organometallics

Using organometallics to make organic molecules

Oxidation of alcohols

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 SOCI2 or PCI5

Making other compounds by substitution reactions of acid derivatives

Making ketones from esters: the problem

Making ketones from esters: the solution

And to conclude

11. Nucleophilic substitution at C=O with loss of carbonyl oxygen

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

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

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

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

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

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

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

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 5 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

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

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

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

22. Conjugate addition and nucleophilic aromatic substitution.

Notes:

Revised edition of: Organic chemistry / Jonathan Clayden [and others].

Includes bibliographical references and index.

ISBN:

9780199270293

0199270295

0191666211

9780191666216

9780199663347

0199663343

OCLC:

761379371

Publisher Number:

6978818