+353-1-416-8900REST OF WORLD
+44-20-3973-8888REST OF WORLD
1-917-300-0470EAST COAST U.S
1-800-526-8630U.S. (TOLL FREE)

PRINTER FRIENDLY

Organic Mechanisms. Reactions, Methodology, and Biological Applications. Edition No. 2

  • ID: 5186239
  • Book
  • March 2021
  • 528 Pages
  • John Wiley and Sons Ltd
1 of 3
This book helps readers move from fundamental organic chemistry principles to a deeper understanding of reaction mechanisms. It directly relates sophisticated mechanistic theories to synthetic and biological applications and is a practical, student-friendly textbook.

Presents material in a student-friendly way by beginning each chapter with a brief review of basic organic chemistry, followed by in-depth discussion of certain mechanisms   Includes end-of-chapter questions in the book and offers an online solutions manual along with PowerPoint lecture slides for adopting instructors   Adds more examples of biological applications appealing to the fundamental organic mechanisms
  • Presents material in a student-friendly way by beginning each chapter with a brief review of basic organic chemistry, followed by in-depth discussion of certain mechanisms
  • Includes end-of-chapter questions in the book and offers an online solutions manual along with PowerPoint lecture slides for adopting instructors
  • Adds more examples of biological applications appealing to the fundamental organic mechanisms
Note: Product cover images may vary from those shown
2 of 3

Preface

Chapter 1 Fundamental Principles

1.1 – Reaction mechanisms and their importance

1.2 – Elementary (concerted) and stepwise reactions

1.3 – Molecularity

1.3.1 – Unimolecular reactions

1.3.2 – Bimolecular reactions

1.4 – Kinetics

1.4.1 – Rate-laws for elementary (concerted) reactions

1.4.2 – Reactive intermediates and the steady-state assumption

1.4.3 – Rate-laws for stepwise reactions

1.5 – Thermodynamics

1.5.1 – Enthalpy, entropy, and free energy

1.5.2 – Reversible and irreversible reactions

1.5.3 – Chemical equilibrium

1.6 – The transition state

                1.6.1 – The transition state

                1.6.2 – The Hammond postulate

                1.6.3 – The Bell-Evans-Polanyi principle

1.7 – Electronic effects and Hammett equation

                1.7.1 – Electronic effects of substituents

                1.7.2 – Hammett equation

1.8 – The molecular orbital theory

1.8.1 – Formation of molecular orbitals from atomic orbitals

1.8.2 – Molecular orbital diagrams

1.8.3 – Resonance stabilization

1.8.4 – Frontier molecular orbitals

1.9 – Electrophiles/nucleophiles versus acids/bases

1.9.1 – Common electrophiles

1.9.2 – Common nucleophiles

1.10 – Isotope labeling 

1.11 – Enzymes: Biological catalysts

1.12 – The green chemistry methodology            

Problems

References

 

Chapter 2 The Aliphatic C–H Bond Functionalization

2.1 – Alkyl radicals: Bonding and their relative stability

2.2 – Radical halogenations of the C–H bonds on sp3-hybridized carbons: Mechanism

         and nature of the transition states

2.3 – Energetics of the radical halogenations of alkanes and their regioselectivity

2.3.1 – Energy profiles for radical halogenation reactions of alkanes

2.3.2 – Regioselectivity for radical halogenation reactions

2.4 – Kinetics of radical halogenations of alkanes

                2.5 – Radical initiators

                2.6 – Transition-metal-compounds catalyzed alkane C–H bond activation and

         functionalization

2.6.1 – The C–H bond activation via agostic bond

2.6.2 – Mechanisms for the C–H bond oxidative functionalization

2.7 – Superacids catalyzed alkane C–H bond activation and functionalization

2.8 – Nitration of aliphatic C–H bonds via the nitronium NO2+ ion

2.9 – Photochemical and thermal C–H bond activation by the oxidative uranyl UO22+(VI)

         cation

2.10 – Enzyme catalyzed alkane C–H bond activation and functionalization: Biochemical

           methods

Problems

References

 

Chapter 3 Functionalization of the Alkene C=C Bond by Electrophilic Additions

3.1  – Markovnikov additions via intermediate carbocations

3.1.1 – Protonation of the alkene C=C p bond by strong acids to form

                carbocations 

3.1.2 – Additions of hydrogen halides (HCl, HBr, and HI) to alkenes: Mechanism,

regiochemistry, and stereochemistry

3.1.3 – Acid and transition-metal catalyzed hydration of alkenes and its

applications

3.1.4 – Acid catalyzed additions of alcohols to alkenes

3.1.5 – Special electrophilic additions of the alkene C=C bond: Mechanistic and

synthetic aspects

                3.1.6 – Electrophilic addition to the C≡C triple bond via a vinyl cation

                                intermediate

3.2  –  Electrophilic addition of hydrogen halides to conjugated dienes

3.3  – Non-Markovnikov radical addition

3.4  – Hydroboration: Concerted, non-Markovnikov syn-addition

3.4.1 – Diborane (B2H6): Structure and properties

3.4.2 – Concerted, non-Markovnikov syn-addition of borane (BH3) to the alkene

C=C bond: Mechanism, regiochemisty and stereochemistry

3.4.3 – Synthesis of special hydroborating reagents

3.4.4 – Reactions of alkenes with special hydroborating reagents: Regiochemistry,

stereochemistry and their applications in chemical synthesis  

3.5  – Transition-metal catalyzed hydrogenation of the alkene C=C bond (syn-addition)

3.5.1 – Mechanism and stereochemistry

3.5.2 – Synthetic applications

3.5.3 – Biochemically related applications: Hydrogenated fats (oils)

3.6  – Halogenation of the alkene C=C bond (Anti-addition): Mechanism and its

          stereochemistry

Problems

References

Chapter 4 Functionalization of the Alkene C=C Bond by Cycloaddition Reactions

4.1 – Cycloadditions of the alkene C=C bond to form three-membered rings

4.1.1 – Epoxidation

4.1.2 – Cycloadditions via carbenes and related species

4.2 – Cycloadditions to form four-membered rings

4.3 – Deals-Alder cycloadditions of the alkene C=C bond to form six-membered rings

4.3.1 – Frontier molecular orbital interactions

4.3.2 – Substituent effects

4.3.3 – Other Diels-Alder reactions

4.4 – 1,3-Dipolar cycloadditions of the C=C and other multiple bonds to form five-

          membered rings

4.4.1 – Oxidation of alkenes by ozone (O3) and osmium tetraoxide (OsO4) via

            cycloadditions

4.4.2 – Cycloadditions of nitrogen-containing 1,3-dipoles to alkenes

4.4.3 – Cycloadditions of the dithionitronium (NS2+) ion to alkenes, alkynes, and

                nitriles: Making CNS-containing aromatic heterocycles

4.5 – Other pericyclic reactions

4.6 – Deals-Alder cycloadditions in water: The green chemistry methods

4.7 – Biological applications

                4.7.1 – Photochemical synthesis of Vitamin D2 via a cyclic transition state

                4.7.2 – Ribosome-catalyzed peptidyl transfer via a cyclic transition state:

                                Biosynthesis of proteins

Problems

References

Chapter 5 The Aromatic C-H bond Functionalization and Related Reactions

5.1 – Aromatic nitration: All reaction intermediates and full mechanism for the aromatic

         C–H bond substitution by nitronium (NO2+) and related electrophiles

5.1.1 – Charge-transfer complex [ArH, NO2+] between arene and nitronium

5.1.2 – Ion-radical pair [ArH+.,NO2.]          

5.1.3 – Arenium [Ar(H)NO2]+ ion

5.1.4 – Full mechanism for aromatic nitration

5.2 – Mechanisms and synthetic utility for aromatic C–H bond substitutions by other

         related electrophiles 

5.3 – The iron (III) catalyzed electrophilic aromatic C–H bond substitution

5.4 – The electrophilic aromatic C–H bond substitution reactions via SN1 and SN2

         mechanisms

5.4.1 – Reactions involving SN1 steps

5.4.2 – Reactions involving SN2 steps

5.5 – Substituent effects on the electrophilic aromatic substitution reactions

5.5.1 – Ortho- and para-directors

5.5.2 – Meta-directors

5.6 – Isomerizations effected by the electrophilic aromatic substitution reactions

5.7 – Electrophilic substitution reactions on the aromatic carbon-metal bonds:

         Mechanisms and synthetic applications

                5.7.1 – Aryl Grignard and aryllithium compounds

                5.7.2 – Ortho-metallation-directing groups (MDGs): Mechanism and synthetic

                                applications

5.8 – Nucleophilic aromatic substitution via a benzyne (aryne) intermediate:

         Functional group transformations on aromatic rings

5.9 – Nucleophilic aromatic substitution via an anionic Meisenheimer complex

5.10 – Biological applications of functionalized aromatic compounds

Problems

References

Chapter 6 Nucleophilic Substitutions on sp3-Hybridized Carbons: Functional Group

      Transformations

6.1 – Nucleophilic substitution on mono-functionalized sp3-hybridized carbon

6.2 – Functional groups which are good and poor leaving groups

6.3 – Good and poor nucleophiles

6.4 – SN2 reactions: Kinetics, mechanism, and stereochemistry

                6.4.1 – Mechanism and stereochemistry for SN2 reactions

6.4.2 – Steric hindrance on SN2 reactions.

                6.4.3 – Effect of nucleophiles

                6.4.4 – Solvent effect

                6.4.5 – Effect of unsaturated groups attached to the functionalized electrophilic

                                carbon

6.5 – Analysis of the SN2 mechanism using symmetry rules and molecular orbital theory

6.5.1The SN2 reactions of methyl and primary haloalkanes RCH2X (X =Cl, Br,

or I; R = H or an Alkyl Group)

6.5.2 – Reactivity of Dichloromethane CH2Cl2

6.6 – SN1 reactions: Kinetics, mechanism, and product development

6.6.1 – The SN1 mechanism and rate law

6.6.2 – Solvent effect

6.6.3 – Effects of carbocation stability and quality of leaving group on the SN1

rates

6.6.4 – Product development for SN1 reactions

6.7 – Competitions between SN1 and SN2 reactions

6.8 – Some useful SN1 and SN2 reactions: Mechanisms and synthetic perspectives

6.8.1 – Nucleophilic substitution reactions effected by carbon nucleophiles.

6.8.2 – Synthesis of primary amines

6.8.3 – Synthetic utility of triphenylphosphine: A strong phosphorus nucleophile

6.8.4 – Neighboring group assisted SN1 reactions

6.8.5 – Nucleophilic substitution reactions of alcohols catalyzed by solid Bronsted

                acids: A green chemistry approach

6.9 – Biological applications of nucleophilic substitution reactions 

6.9.1 – Biomedical applications

6.9.2 – Glycoside hydrolases: Enzymes catalyzing hydrolytic cleavage of the

glycosidic bonds by the SN2–like reactions

6.9.3 – Biosynthesis involving nucleophilic substitution reactions

6.9.4 – An enzyme-catalyzed nucleophilic substitution of an haloalkane

Problems

References

Chapter 7 Eliminations

7.1 – E2 Elimination: Bimolecular b-elimination of H/LG and its regiochemistry and

stereochemistry

7.1.1 – Mechanism and regiochemistry

7.1.2 – E2 eliminations of functionalized cycloalkanes

7.1.3 – Stereochemistry

7.2 – Analysis of the E2 mechanism using symmetry rules and molecular orbital theory

                7.2.1 – Chain-like haloalkanes

                7.2.2 – Halocyclohexane

                7.2.3 – Quantitative theoretical studies of E2 reactions

7.3 – Basicity versus nucleophilicity for various anions

7.4 – Competition of E2 and SN2 reactions

7.5 – E1 Elimination: Stepwise b-elimination of H/LG via an intermediate carbocation

         and its rate-law

7.5.1 – Mechanism and rate law

7.5.2 – E1 dehydration of alcohols

7.6 – Energy profiles for E1 reactions

7.6.1 – The Bell-Evens-Polanyi Principle

7.6.2 – The E1 dehydration of alcohols (ROH)

7.6.3 – The E1 dehydrohalogenation of haloalkanes (RX, X = Cl, Br, or I)

7.7 – The E1 elimination of ethers

7.8 – Intramolecular (unimolecular) eliminations via a cyclic transition state

                7.8.1 – Concerted, syn-elimination of esters

7.8.2 – Selenoxide elimination

7.8.3 – Silyloxide elimination

7.8.4 – Unimolecular elimination of hydrogen halide from haloalkanes 

7.9 – Mechanisms for reductive elimination of LG1/LG2 (two functional groups) on

         adjacent carbons

7.10 – The a-Elimination giving a carbene: A mechanistic analysis using symmetry rules

                and molecular orbital theory

                7.10.1 – The bimolecular a-elimination of trichloromethane (CHCl3) giving

              dichlorocarbene (CCl2)

7.10.2 – Formation of a carbene by unimolecular a-elimination of a haloalkane

                  and the subsequent rearrangement to an alkene via a C–H (C–D) bond

                  elimination  

7.11 – E1cb elimination

7.12 – Biological applications: Enzyme-catalyzed biological elimination reactions

7.12.1 – The enzyme-catalyzed b-oxidation of fatty acyl coenzyme A

7.12.2 – Elimination reactions involved in biosynthesis

Problems

References

Chapter 8 Nucleophilic Additions and Substitutions on Carbonyl Groups

8.1 – Nucleophilic additions and substitutions of carbonyl compounds

8.2 – Nucleophilic additions of aldehydes and ketones and their biological applications

8.2.1 – Acid and base catalyzed hydration of aldehydes and ketones

8.2.2 – Acid catalyzed nucleophilic additions of alcohols to aldehydes and

                ketones

8.2.3 – Biological applications: Cyclic structures of carbohydrates

8.2.4 – Addition of sulfur nucleophile to aldehydes

8.2.5 – Nucleophilic addition of amines to ketones and aldehydes

8.2.6 – Nucleophilic additions of hydride donors to aldehydes and ketones:

            Organic reductions and mechanisms

8.3 – Biological hydride donors NAD(P)H and FADH2

8.4 – Activation of carboxylic acids via nucleophilic substitutions on the carbonyl

         carbons

8.4.1 – Reactions of carboxylic acids with thionyl chloride

8.4.2 – Esterification reactions, synthetic applications, and green chemistry

                methods

8.4.3 – Formation of anhydrides

8.4.4 – Nucleophilic addition to alkyllithium

8.5 – Nucleophilic substitutions of acyl derivatives and their biological applications

8.5.1 – Nucleophilic substitutions of acyl chlorides and anhydrides

8.5.2 – Hydrolysis and other nucleophilic substitutions of esters

8.5.3 – Biodiesel synthesis and reaction mechanism        

8.5.4 – Biological applications: Mechanisms for serine-type hydrolases

8.6 – Reduction of acyl derivatives by hydride donors

8.7 – Kinetics of the Nucleophilic addition and substitution of acyl derivatives

Problems            

References

Chapter 9 Reactivity of the a-Hydrogen to Carbonyl Groups

9.1 – Formation of enolates and their nucleophilicity

9.1.1 – Formation of enolates

9.1.2 – Molecular orbitals and nucleophilicity of enolates

9.2 – Alkylation of carbonyl compounds (aldehydes, ketones, and esters) via enolates and

         hydrazones

9.2.1 – Alkylation via enolates

9.2.2 – Alkylation via hydrazones and enamines

9.3 – Aldol reactions

9.3.1 – Mechanism and synthetic utility

9.3.2 – Stereoselectivity

9.3.3 – Other synthetic applications

9.4 – Acylation reactions of esters via enolates: Mechanism and synthetic utility

9.5 – Biological applications: Roles of enolates in metabolic processes in living

         organisms

                9.5.1 – The citric acid cycle and mechanism for citrate synthase

                9.5.2 – Ketogenesis and thiolase

Problems

References

Chapter 10 Rearrangements

10.1 – Major types of rearrangements

10.2 – Rearrangement of carbocations: 1,2-Shift

10.2.1 – 1,2-Shifts in carbocations produced from acyclic molecules

10.2.2 – 1,2-Shifts in carbocations produced from cyclic molecules – Ring

  expansion

10.2.3 – Resonance stabilization of carbocation – Pinacol rearrangement

10.2.4 – In vivo cascade carbocation rearrangements: Biological significance  

10.2.5 – Acid catalyzed 1,2-shift in epoxides

10.2.6 – Anion initiated 1,2-shift

10.3 – Neighboring leaving group facilitated 1,2-rearrangement

10.3.1 – Beckmann rearrangement

10.3.2 – Hofmann rearrangement

10.3.3 – Baeyer-Villiger oxidation (rearrangement)

10.3.4 – Acid catalyzed rearrangement of organic peroxides

10.4 – Carbene rearrangement: 1,2-Rearrangement of hydrogen facilitated by a lone pair

           of electrons

10.5 – Claisen rearrangement

10.6 – Claisen rearrangement in water: The green chemistry methods

10.7 – Photochemical isomerization of alkenes and its biological applications 

10.7.1 – Photochemical isomerization

10.7.2 – Biological relevance

10.8 – Rearrangement of carbon-nitrogen-sulfur containing heterocycles

Problems

References

Note: Product cover images may vary from those shown
3 of 3
Xiaoping Sun
Note: Product cover images may vary from those shown
Adroll
adroll