S/G & S/M Organic Chem

This innovative book from acclaimed educator Paula Bruice is organized in a way that discourages rote memorization. The author’s writing has been praised for anticipating readers' questions, and appeals to their need to learn visually and by solving problems. Emphasizing that learners should reason their way to solutions rather than memorize facts, Bruice encourages them to think about what they have learned previously and apply that knowledge in a new setting. KEY TOPICS The book balances coverage of traditional topics with bioorganic chemistry, highlights mechanistic similarities, and ties synthesis and reactivity together—teaching the reactivity of a functional group and the synthesis of compounds obtained as a result of that reactivity. For the study of organic chemistry.

Paula Yurkanis Bruice was raised primarily in Massachusetts, Germany, and Switzerland and was graduated from the Girls' Latin School in Boston. She received an A.B. from Mount Holyoke College and a Ph.D. in chemistry from the University of Virginia. She received an NIH postdoctoral fellowship for study in biochemistry at the University of Virginia Medical School, and she held a postdoctoral appointment in the Department of Pharmacology at Yale Medical School.

She is a member of the faculty at the University of California, Santa Barbara, where she has received the Associated Students Teacher of the Year Award, the Academic Senate Distinguished Teaching Award, and two Mortar Board Professor of the Year Awards. Her research interests concern the mechanism and catalysis of organic reactions, particularly those of biological significance. Paula has a daughter and a son who are physicians and a son who is a lawyer. Her main hobbies are reading mystery/suspense novels and her pets (three dogs, two cats, and a parrot).

PART I:  AN INTRODUCTION TO THE STUDY OF ORGANIC CHEMISTRY

CHAPTER 1.  ELECTRONIC STRUCTURE AND BONDING · ACIDS AND BASES

            1.1       The Structure of an Atom

            1.2       How the Electrons in an Atom are Distributed

            1.3       Ionic and Covalent Bonds

                                    Ionic Bonds are Formed by the Transfer of Electrons

                                    Covalent Bonds are Formed by Sharing Electrons

                                    Polar Covalent Bonds

1.4       How the Structure of a Compound is Represented

                                    Lewis Structures

                                    Kekule Structures

                                    Condensed Structures

            1.5       Atomic Orbitals

            1.6       An Introduction to Molecular Orbital Theory

1.7       How Single Bonds are Formed in Organic Compounds

                                    The Bonds in Methane

                                    The Bonds in Ethane

            1.8       How a Double Bond is Formed: The Bonds in Ethene

            1.9       How a Triple Bonds is Formed: The Bonds in Ethyne

            1.10     The Bonds in the Methyl Cation, the Methyl Radical, and the Methyl Anion

                                    The Methyl Cation

                                    The Methyl Radical

                                    The Methyl Anion

            1.11     The Bonds in Water

            1.12     The Bonds in Ammonia and in the Ammonium Ion

            1.13     The Bonds in the Hydrogen Halides

            1.14     Summary: Hybridization, Bond Lengths, Bond Strengths, and Bond Angles

            1.15     The Dipole Moments of Molecules

1.16     An Introduction to Acids and Bases

1.17     pK_a and pH

1.18     Organic Acids and Bases

1.19     How to Predict the Outcome of an Acid-Base Reaction

1.20     How the Structure of an Acid Affects Its Acidity

1.21     How Substituents Affect the Strength of an Acid

1.22    An Introduction to Delocalized Electrons

1.23    A Summary of the Factors that Determine Acid Strength

1.24    How the pH Affects the Structure of an Organic Compound

1.25    Buffer Solutions

            1.26    The Second Definition of Acid and Base: Lewis Acids and Bases

CHAPTER 2.  AN INTRODUCTION TO ORGANIC COMPOUNDS

NOMENCLATURE,  PHYSICAL PROPERTIES, AND REPRESENTATION OF STRUCTURE

            2.1       How Alkyl Substituents are Named

            2.2       Nomenclature of Alkanes

            2.3       Nomenclature of Cycloalkanes

            2.4       Nomenclature of Alkyl Halides

            2.5       Nomenclature of Ethers

            2.6       Nomenclature of Alcohols

            2.7       Nomenclature of Amines

2.8       The Structures of Alkyl Halides, Alcohols, Ethers, and Amines

2.9       The Physical Properties of Alkanes, Alkyl Halides, Alcohols, Ethers, and Amines

Boiling Points

Melting Points

Solubility

            2.10     Rotation Occurs About Carbon-Carbon Bonds

            2.11     Some Cycloalkanes Have Ring Strain

            2.12     Conformations of Cyclohexane

            2.13     Conformers of Monosubstituted Cyclohexanes

            2.14     Conformers of Disubstituted Cyclohexanes

PART II:  ELECTROPHILIC ADDITION REACTIONS, STEREOCHEMISTRY, AND ELECTRON DEELOCALIZATION

CHAPTER 3.  ALKENES: STRUCTURE, NOMENCLATURE AND AN INTRODUCTION TO

  REACTIVITY · THERMODYNAMICS AND KINETICS

            3.1       Molecular Formulas and the Degree of Unsaturation

            3.2       Nomenclature of Alkenes

            3.3       The Structures of Alkenes

            3.4       Alkenes Can Have Cis and Trans Isomers

            3.5       Naming Alkenes Using the E,Z System

            3.6       How Alkenes React · Curved Arrows Show the Flow of Electrons

            3.7       Thermodynamics and Kinetics

                                    A Reaction Coordinate Diagram Describes the Reaction Pathway

                                    Thermodynamics: How Much Product Is Formed?

                                    Kinetics: How Fast Is the Product Formed?

3.8       Using a Reaction Coordinate Diagram to Describe a Reaction

CHAPTER 4.  THE REACTIONS OF ALKENES

            4.1       Addition of a Hydrogen Halide to an Alkene

4.2       Carbocation Stability Depends on the Number of Alkyl Groups Attached to the Positively Charged Carbon

4.3       The Structure of the Transition State Lies Partway Between the Structures of the Reactants and Products

4.4       Electrophilic Addition Reactions Are Regioselective

4.5       Acid-Catalyzed Addition Reactions

Addition of Water to an Alkene

Addition of an Alcohol to an Alkene

            4.6       A Carbocation will Rearrange if It Can Form a More Stable Carbocation

4.7       Addition of a Halogen to an Alkene

            4.8       Oxymercuration-Demercuration: Are Other Ways to Add Water or Alcohol to an Alkene

4.9       Addition of a Peroxyacid to an Alkene

4.10     Addition of Borane to an Alkene: Hydroboration-Oxidation

            4.11     Addition of Hydrogen to an Alkene · The Relative Stabilities of Alkenes

            4.12     Reactions and Synthesis

CHAPTER 5.  STEREOCHEMISTRY 

 THE ARRANGEMENT OF ATOMS IN SPACE;

             THE STEREOCHEMISTRY OF ADDITION REACTIONS

            5.1       Cis-Trans Isomers Result From Restricted Rotation

5.2       A Chiral Object has a Nonsuperimposable Mirror Image

5.3       An Asymmetric Center Is a Cause of Chirality In a Molecule

5.4       Isomers with One Asymmetric Center

5.5       Asymmetric Centers and Stereocenters

            5.6       How to Draw Enantiomers       

            5.7       Naming Enantiomers by the R,S System

            5.8       Chiral Compounds are Optically Active

5.9       How Specific Rotation is Measured

5.10     Enantiomeric Excess

            5.11     Isomers with More than One Asymmetric Center

            5.12     Meso Compounds Have Asymmetric Centers but are Optically Inactive

            5.13     How to Name Isomers with More than One Asymmetric Center

5.14     Reactions of Compounds that Contain a Asymmetric Center

5.15     The Absolute Configuration of (+)-Glyceraldehyde

5.16     How Enantiomers Can be Separated

            5.17     Nitrogen and Phosphorous Atoms Can be Asymmetric Centers

            5.18     The Stereochemistry of Reactions:  Regioselective, Stereoselective, and Stereospecific Reactions

            5.19     The Stereochemistry of Electrophilic Addition Reactions of Alkenes 

                                    Addition Reactions that Form a Product with One Asymmetric Center

                                    Addition Reactions that Form Products with Two Asymmetric Centers

                                                Addition Reactions that Form a Carbocation Intermediate

                                                The Stereochemistry of Hydrogen Addition

                                                The Stereochemistry of Peroxyacid Addition

                                                The Stereochemistry of Hydroboration-Oxidation

                                                Addition Reactions that Form a Cyclic Bromonium Ion Intermediate

5.20     The Stereochemistry of Enzyme-Catalyzed Reactions

5.21     Enantiomers can be Distinguished by Biological Molecules

                        Enymes

                        Receptors

CHAPTER 6.     THE REACTIONS OF ALKYNES · AN INTRODUCTION TO MULTISTEP SYNTHESIS

            6.1       The Nomenclature of Alkynes

6.2       How to Name a Compound That Has More than One Functional Group

6.3       The Physical Properties of Unsaturated Hydrocarbons

            6.4       The Structure of Alkynes

            6.5       How Alkynes React

            6.6       Addition of Hydrogen Halides and Addition of Halogens to an Alkyne

6.7       Addition of Water to an Alkyne

            6.8       Addition of Borane to an Alkyne: Hydroboration-Oxidation

6.9       Addition of Hydrogen to an Alkyne

6.10     A Hydrogen Bonded to an sp Carbon is “Acidic”         

            6.11     Synthesis Using Acetylide Ions

            6.12     Designing a Synthesis I:  An Introduction to Multistep Synthesis

CHAPTER 7.  DELOCALIZED ELECTRONS AND THEIR EFFECT ON STABILITY,   

 REACTIVITY, AND pKa · MORE ABOUT MOLECULAR ORBITAL THEORY

            7.1       Benzene Has Delocalized Electrons

            7.2       The Bonding in Benzene

            7.3       Resonance Contributors and the Resonance Hybrid

            7.4       How to Draw Resonance Contributors

            7.5       The Predicted Stabilites of Resonance Contributors

7.6       Delocalization Energy Is the Additional Stability Delocalized Electrons Give to a Compound

7.7       Examples That Illustrate the Effect of Delocalized Electrons on Stability

Stability of Dienes

Stability of Allylic and Benzylic Cations

            7.8       A Molecular Orbital Description of Stability     

1,3-Butadiene and 1,4-Pentadiene

1,3,5-Hexatriene and Benzene

7.9       How Delocalized Electrons Affect pKa

7.10     Delocalized Electrons Can Affect the Product of a Reaction

                        Reactions of Isolated Dienes

Reactions of Conjugated Dienes

7.11     Thermodynamic versus Kinetic Control of Reactions

            7.12     The Diels-Alder Reaction Is a 1,4-Addition Reaction

                                    A Molecular Orbital Description of the Diels-Alder Reaction

                                    Predicting the Product When Both Reagents Are Unsymmetrically Substituted

                                    Conformations of the Diene

                                    The Stereochemistry of the Diels-Alder Reaction

PART III:  SUBSTITUTION AND ELIMINATION REACTIONS

CHAPTER 8.  SUBSTITUTION REACTIONS OF OF ALKYL HALIDES

            8.1       How Alkyl Halides React

            8.2       The Mechanism of an SN2 Reaction

            8.3       Factors that Affect SN2 Reactions

The Leaving Group

The Nucleophile

Nucleophilicity is Affected by the Solvent

Nucleophilicity is Affected by Steric Effects

8.4       The Reversibility of an SN2 Reaction Depends on the Basicities of the Leaving Groups in   the Forward and Reverse Directions

            8.5       The Mechanism of an SN1 Reaction

            8.6       Factors that Affect an SN1 Reaction

The Leaving Group

The Nucleophile

Carbocation Rearrangements

8.7       More About the Stereochemistry of SN2 and SN1 Reactions

Stereochemistry of SN2 Reactions

Stereochemistry of SN1 Reactions

            8.8       Benzylic Halides, Allylic Halides, Vinylic Halides, and Aryl Halides

            8.9       Competition Between SN2 and SN1 Reactions

8.10     The Role of the Solvent in SN2 and SN1 Reactions

How a Solvent Affects Reaction Rates in General

How a Solvent Affects the Rate of an SN1 Reaction

How a Solvent Affects the Rate of an SN2 Reaction

            8.11     Biological Methylating Reagents Have Good Leaving Groups

CHAPTER 9.    ELIMINATION REACTIONS OF ALKYL HALIDES · COMPETITION BETWEEN SUBSTITUTION AND ELIMINATION

            9.1       The E2 Reaction

            9.2       An E2 Reaction is Regioselective

            9.3       The E1 Reaction

            9.4       Competition Between E2 and E1 Reactions

9.5       E2 and E1 Reactions are Stereoselective

The Stereoisomers Formed in an E2 Reaction

The Stereoisomers Formed in an E1 Reaction

9.6       Elimination from Substituted Cyclohexanes

E2 Reactions of Substituted Cyclohexanes

E1 Reactions of Substituted Cyclohexanes

9.7       A Kinetic Isotope Effect Can Help Determine a Mechanism

9.8       Competition Between Substitution and Elimination

SN2/E2 Conditions

SN1/E1 Conditions

9.9       Substitution and Elimination Reactions in Synthesis

Using Substitution Reactions to Synthesize Compounds

Using Elimination Reactions to Synthesize Compounds

            9.10     Consecutive E2 Elimination Reactions

9.11     Intermolecular Versus Intramolecular Reactions

9.12     Designing a Synthesis II: Approaching the Problem

CHAPTER 10.  REACTIONS OF ALCOHOLS, AMINES, ETHERS, EXPOXIDES, AND SULFUR-CONTAINING COMPOUNDS · ORGANOMETALLIC COMPOUNDS

10.1     Nucleophilic Substitution Reactions of Alcohols: Forming Alkyl Halides

10.2     Other Methods for Converting Alcohols into Alkyl Halides

10.3     Converting Alcohols into Sulfonate Esters

10.4     Elimination Reactions of Alcohols: Dehydration

10.5     Oxidation of Alcohols

10.6     Amines do not Undergo Substitution or Elimination Reactions but Are the Most Common Organic Bases

            10.7     Nucleophilic Substitution Reactions of Ethers

            10.8     Nucleophilic Substitution Reactions of Epoxides

10.9     Arene Oxides

10.10   Crown Ethers

            10.11   Thiols, Sulfides, and Sulfonium Salts

10.12   Organometallic Compounds

10.13   Coupling Reactions

CHAPTER 11.  RADICALS · REACTIONS OF ALKANES

            11.1     Alkanes are Unreactive Compounds

11.2     Chlorination and Bromination of Alkanes

11.3     Radical Stability Depends on the Number of Alkyl Groups Attached to the Carbon with the Unpaired Electron

            11.4     The Distribution of Products Depends on Probability and Reactivity

11.5     The Reactivity-Selectivity Principle

11.6     Addition of Radicals to an Alkene

            11.7     Stereochemistry of Radical Substitution and Addition Reactions

11.8     Radical Substitution of Benzylic and Allylic Hydrogens

            11.9     Designing a Synthesis III: More Practice with Multistep Synthesis

            11.10   Radical Reactions Occur in Biological Systems

            11.11   Radicals and Stratospheric Ozone

PART IV:  IDENTIFICATION OF ORGANIC COMPOUNDS

CHAPTER 12.  MASS SPECTROMETRY, INFRARED SPECTROSCOPY, AND ULTRAVIOLET/VISIBLE SPECTROSCOPY

            12.1     Mass Spectrometry

            12.2     The Mass Spectrum.  Fragmentation    

            12.3     Isotopes in Mass Spectrometry

            12.4     High-Resolution Mass Spectrometry Can Determine Molecular Formulas

12.5     Fragmentation Patterns of Functional Groups

Alkyl Halides

Ethers

Alcohols

Ketones

            12.6     Spectroscopy and the Electromagnetic Spectrum

12.7     Infrared Spectroscopy

Obtaining an Infrared Spectrum

The Functional Group and Fingerprint Regions

            12.8     Characteristic Infrared Absorption Bands

            12.9     The Intensity of Absorption Bands

12.10   The Position of Absorption Bands

Hooke’s Law

The Effect of Bond Order

12.11   The Position of an Absorption Band is Affected by Electron Delocalization, Electron Donation and Withdrawal, and Hydrogen Bonding

O–GH Absorption Bands

C–H Absortion Bands

12.12   The Shape of Absorption Bands

            12.13   The Absence of Absorption Bands

            12.14   Some Vibrations are Infrared Inactive

12.15   A Lesson in Interpreting Infrared Spectra

            12.16   Ultraviolet and Visible Spectroscopy

            12.17   The Beer-Lambert Law

            12.18   The Effect of Conjugation on l_max

            12.19   The Visible Spectrum and Color

            12.20   Uses of UV/Vis Spectroscopy

CHAPTER 13.  NMR SPECTROSCOPY

            13.1     An Introduction to NMR Spectroscopy

            13.2     Fourier Transform NMR

            13.3     Shielding Causes Different Hydrogens to Show Signals at Different Frequencies

            13.4     The Number of Signals in an ¹H NMR Spectrum

13.5     The Chemical Shift Tells How Far the Signal Is from the Reference Signal

13.6     The Relative Positions of ¹H NMR Signals

13.7     Characteristic Values of Chemical Shifts

            13.8     Diamagnetic Anisotropy

13.9     The Integration of NMR Signals Reveals the Relative Number of Protons Causing the Signal

13.10   Splitting of the Signals is Desribed by the N+1 Rule

13.11   More Examples of ¹H NMR Spectra

            13.12   Coupling Constants Identify Coupled Protons

13.13   Splitting Diagrams Explain the Multiplicity of a Signal

            13.14   The Time Dependence of NMR Spectroscopy

            13.15   Protons Bonded to Oxygen and Nitrogen

            13.16   The Use of Deuterium in ¹H NMR Spectroscopy

            13.17   The Resolution of ¹H NMR Spectra

            13.18   ¹³C NMR Spectroscopy

            13.19   DEPT ¹³C NMR Spectra

            13.20   Two-Dimensional NMR Spectroscopy

            13.21   NMR Used in Medicine is Called Magnetic Resonance Imaging

PART V:  AROMATIC COMPOUNDS

CHAPTER 14.  AROMATICITY · REACTIONS OF BENZENE

14.1     Aromatic Compounds are Unusually Stable

14.2     The Two Criteria for Aromaticity

            14.3     Applying the Criteria for Aromaticity

            14.4     Aromatic Heterocyclic Compounds

            14.5     Some Chemical Consequences of Aromaticity

            14.6     Antiaromaticity

            14.7     A Molecular Orbital Description of Aromaticity and Antiaromaticity

14.8     Nomenclature of Monosubstituted Benzenes

14.9     How Benzene Reacts

            14.10   General Mechanism for Electrophilic Aromatic Substitution Reactions

            14.11   Halogenation of Benzene

            14.12   Nitration of Benzene

            14.13   Sulfonation of Benzene

            14.14   Friedel-Crafts Acylation of Benzene

            14.15   Friedel-Crafts Alkylation of Benzene

14.16   Alkylation of Benzene by Acylation-Reduction

14.17   Using Coupling Reactions to Alkylate Benzene

14.18   It is important to Have More than One Way to Carry Out a Reaction

14.19   How Some Substituents on a Benzene Ring Can Be Chemically Changed

CHAPTER 15.  REACTIONS OF SUBSTITUTED BENZENES

            15.1     Nomenclature of Disubstituted and Polysubstituted Benzenes

15.2     Some Substituents Increase the Reactivity of a Benzene Ring and Some Decrease Its Reactivity

        Inductive Electron Withdrawal

        Electron Donation by Hyperconjugation

        Resonance Electron Donation and Withdrawal

        Relative Reactivity of Substituted Benzenes

            15.3     The Effect of Substituents on Orientation

            15.4     The Effect of Substituents on pKa

            15.5     The Ortho/Para Ratio

            15.6     Additional Considerations Regarding Substituent Effects

            15.7     Designing a Synthesis III:  Synthesis of Monosubstituted and Disubstituted Benzenes     

            15.8     Synthesis of Trisubstituted Benzenes

            15.9     Synthesis of Substituted Benzenes Using Arenediazonium Salts

            15.10   The Arenediazonium Ion as an Electrophile

            15.11   Mechanism for the Reaction of Amines with Nitrous Acid

            15.12   Nucleophilic Aromatic Substitution: An Addition-Elimination Mechanism

15.13   Nucleophilic Aromatic Substitution: An Elimination-Addition Mechanism that Forms a Benzyne Intermediate

            15.14   Polycyclic Benzenoid Hydrocarbons

PART VI:  CARBONYL COMPOUNDS 

CHAPTER 16.  CARBONYL COMPOUNDS I: NUCLEOPHILIC ACYL SUBSTITUTION

            16.1     Nomenclature of Carboxylic Acids and Caboxylic Acid Derivatives

            16.2     Structures of Carboxylic Acids and Carboxylic Acid Derivatives

            16.3     Physical Properties of Carbonyl Compounds

            16.4     Naturally Occurring Carboxylic Acids and Carboxylic Acid Derivatives

            16.5     How Class I Carbonyl Compounds React

16.6     Relative Reactivities of Carboxylic Acids and Carboxylic Acid Derivatives

16.7     General Mechanism for Nucleophilic Acyl Substitution Reactions

            16.8     Reactions of Acyl Halides

            16.9     Reactions of Acid Anhydrides

            16.10   Reactions of Esters

16.11   Acid-Catalyzed Ester Hydrolysis

16.12   Hydroxide-Ion Promoted Ester Hydrolysis

16.13   How the Mechanism for Nucleophilic Acyl Substitution Reactions Was Confirmed

16.14   Soaps, Detergents, and Micelles

            16.15   Reactions of Carboxylic Acids 

            16.16   Reactions of Amides

16.17   The Hydrolysis of Amides Is Catalyzed by Acids

16.18   Hydrolysis of an Imide: A Way to Synthesize Primary Amines

16.19   Hydrolysis of Nitriles

16.20   Designing a Synthesis V: The Synthesis of Cyclic Compounds

            16.21   How Chemists Activate Carboxylic Acids

            16.22   How Cells Activate Carboxylic Acids

            16.23   Dicarboxylic Acids and Their Derivatives

CHAPTER 17. CARBONYL COMPOUNDS II:

            17.1     Nomenclature of Aldehydes and Ketones

            17.2     Relative Reactivities of Carbonyl Compounds

            17.3     How Aldehydes and Ketones React

            17.4     Reactions of Carbonyl Compounds with Grignard Reagents

            17.5     Reactions of Carbonyl Compounds with Acetylide Ions

            17.6     Reactions of Carbonyl Compounds with Hydride Ion

            17.7     Reactions of Aldehydes and Ketones with Hydrogen Cyanide

            17.8     Reactions of Aldehydes and Ketones with Amines and Derivatives of Amines

            17.9     Reactions of Aldehydes and Ketones with Water

            17.10   Reactions of Aldehydes and Ketones with Alcohols

            17.11   Protecting Groups

17.12   Addition of Sulfur Nucleophiles

17.13   The Wittig Reaction Forms an Alkene

            17.14   Stereochemistry of Nucleophilic Addition Reactions: Re and Si Faces

17.15   Designing a Synthesis VI: Disconnections, Synthons, and Synthetic Equivalents

17.16   Nucleophilic Addition to a,b-Unsaturated Aldehydes and Ketones

17.17   Nucleophilic Addition to a,b-Unsaturated Carboxylic Acid Derivatives

17.18   Enzyme-Catalyzed Additions to a,b-Unsaturated Carbonyl Compounds

CHAPTER 18.  CARBONYL COMPOUNDS III: REACTIONS AT THE a-CARBON

            18.1     Acidity of an a-Hydrogens

            18.2     Keto-Enol Tautomers

18.3     Enolization

18.4     How Enols and Enolate Ions React

            18.5     Halogenation of the a-Carbon of Aldehydes and Ketones.

Acid-Catalyzed Halogenation

Base-Promoted Halogenation

The Haloform Reaction

            18.6     Halogenation of the a-Carbon of Carboxylic Acids:  The Hell-Volhard-Zelinski Reaction

            18.7     a-Halogenated Carbonyl Compounds Are Useful in Synthesis

            18.8     Using Lithium Diisopropylamide (LDA) to Form an Enolate

            18.9     Alkylation of the a-Carbon of Carbonyl Compounds

            18.10   Alkylation and Acylation of the a-Carbon Using an Enamine Intermediate

            18.11   Alkylation of the b-Carbon: The Michael Reaction

            18.12   An Aldol Addition Forms b-Hydroxyaldehydes or b -Hydroxyketones

            18.13   Dehydration of Aldol Addition Products Forms a,b-Unsaturated Aldehydes and Ketones

            18.14   The Mixed Aldol Addition

            18.15   A Claisen Condensation Forms a b-Keto Ester

            18.16   The Mixed Claisen Condensation

            18.17   Intramolecular Condensation and Addition Reactions

Intramolecular Claisen Condensations

Intramolecular Aldol Additions

The Robinson Annulation

            18.18   3-Oxocarboxylic Acids Can Be Dehydrated

            18.19   The Malonic Ester Synthesis: A Way to Snthesize a Carboxylic Acid

            18.20   The Acetoacetic Ester Synthesis: A Way Synthesize a Methyl Ketone

            18.21   Designing a Synthesis VII:  Making New Carbon-Carbon Bonds

18.22   Reactions at the a-Carbon in Biological Systems

A Biological Aldol Condensation

A Biological Claisen Condensation

A Biological Decarboxylation

PART VII:  OXIDATION-REDUCTION REACTIONS AND AMINES

CHAPTER 19. MORE ABOUT OXIDATION-REDUCTION REACTIONS

            19.1     Reduction Reactions

Reduction by Addition of Two Hydrogen Atoms

Reduction by Addition of an Electron, a Proton, an Electron, and a Proton

Reduction by Addition of a Hydride Ion and a Proton

            19.2     Oxidation of Alcohols

19.3     Oxidation of Aldehydes and Ketones

19.4     Designing a Synthesis VIII: Controlling Stereochemistry

            19.5     Hydroxylation of Alkenes

            19.6     Oxidative Cleavage of 1,2-Diols

            19.7     Oxidative Cleavage of Alkenes

            19.8     Oxidative Cleavage of Alkynes

            19.9     Designing a Synthesis IX:  Functional Group Interconversion

CHAPTER 20.  MORE ABOUT AMINES. HETEROCYCLIC COMPOUNDS

            20.1     More About Amine Nomenclature

            20.2     Amines Invert Rapidly

20.3     More About the Acid-Base Properties of Amines

20.4     Amines React as Bases and as Nucleophiles

20.5     Quaternary Ammonium Hydroxides Undergo Elimination Reactions

            20.6     Phase-Transfer Catalysis

20.7     Oxidation of Amines: The Cope Elimination Reaction

            20.8     Synthesis of Amines

            20.9     Aromatic Five-Membered Ring Heterocycles                           

            20.10   Aromatic Six-Membered-Ring Heterocycles                            

            20.11   Amine Heterocycles Have Important Roles in Nature                                       

PART VIII:  BIOORGANIC COMPOUNDS

CHAPTER 21.  CARBOHYDRATES

            21.1     Classification of Carbohydrtes

            21.2     The D and L Notation

            21.3     Configurations of the Aldoses

            21.4     Configurations of the Ketoses

            21.5     Reactions of Monosaccharides in Basic Solutions

21.6     Redox Reactions of Monosaccharides

21.7     Monosaccharides Form Crystalline Osazones

21.8     Lengthening the Chain: The Kiliani—Fischer Synthesis

21.9     Shortening the Chain: The Wohl Degradation

            21.10   Stereochemistry of Glucose: the Fischer Proof  

            21.11   Monosaccharides Form Cyclic Hemiacetals

            21.12   Glucose Is the Most Stable Aldohexose

21.13   Acylation and Alkylation of Monosaccharides

21.14   Formation of Glycosides

            21.15   The Anomeric Effect

21.16   Reducing and Nonreducing Sugars

21.17   Determination of Ring Size

21.18   Disaccharides

            21.19   Polysaccharides

            21.20   Some Naturally Occurring Products Derived from Carbohydrates

            21.21   Carbohydrates on Cell Surfaces

            21.22   Synthetic Sweeteners

CHAPTER 22.  AMINO ACIDS, PEPTIDES, AND PROTEINS

            22.1     Classification and Nomenclature of Amino Acids

            22.2     Configuration of the Amino Acids

            22.3     Acid-Base Properties of Amino Acids

            22.4     The Isoelectric Point

            22.5     Separation of Amino Acids

            22.6     Resolution of Racemic Mixtures of Amino Acids

            22.7     Peptide Bonds and Disulfide Bonds

            22.8     Some Interesting Peptides

            22.9     The Strategy of Peptide Bond Synthesis: N-Protection and C-Activation

            22.10   Automated Peptide Synthesis

            22.11   An Introduction to Protein Structure

            22.12   How to Determine the Primary Structure of a Peptide or a Protein

            22.13   Secondary Structure of Proteins

            22.14   Tertiary Structure of Proteins

            22.15   Quaternary Structure of Proteins

            22.16   Protein Denaturation

CHAPTER 23.  CATALYSIS                                                                                               

            23.1     Catalysis in Organic Reactions                                                 

            23.2     Acid Catalysis

23.3     Base Catalysis                                                                         

            23.4     Nucleophilic Catalysis

23.5     Metal-Ion Catalysis                                                                             

23.6     Intramolecular Reactions                                                                      

            23.7     Intramolecular Catalysis                                                                       

23.8     Catalysis in Biological Reactions                                                           

23.9     Enzyme-Catalyzed Reactions

                                    Mechanism for Carboxypeptidase A                                        

                                    Mechanism for Serine Proteases                                              

                                    Mechanism for Lysozyme

                                    Mechanism for Glucose-6-phosphate Isomerase                                                          

                                    Mechanism of Aldolase                                    

CHAPTER 24.  THE ORGANIC MECHANISMS OF THE COENZYMES      

            24.1     An Introduction to Metabolism                                     

            24.2     The Vitamin Needed for Many Redox Reactions: Vitamin B₃                           

24.3     Flavin Adenine Dinucleotide and Flavin Mononucleotide: Vitamin B₂    

            23.4     Thiamine Pyrophosphate: Vitamin B₁                                                                           

            23.5     Biotin: Vitamin H                                                         

            24.6     Pyridoxal Phosphate: Vitamin B₆                                                                                              

            24.7     Coenzyme B₁₂: Vitamin B₁₂                                                                

24.8     Tetrahydrofolate: Folic Acid

24.9     Vitamin KH₂: Vitamin K                                                                                              

CHAPTER 25: THE CHEMISTRY OF METABOLISM

25.1     The Four Stages of Catabolism

25.2     ATP Is the Carrier of Chemical Energy

25.3     There Are Three Mechanisms for Phosphoryl Transfer Reactions

25.4     The “High-Energy” Character of Phosphoanhydride Bonds

25.5     Why ATP Is Kinetically Stable in a Cell

25.6     The Catabolism of Fats

25.7     The Catabolism of Carbohydrates

25.8     The Fates of Pyruvate

25.9     The Catabolism of Proteins

25.10   The Citric Acid Cycle

25.11   Oxidative Phosphorylation

25.12   Anabolism

CHAPTER 26.  LIPIDS                                                                                           

            26.1     Fatty Acids Are Long-Chain Carboxylic Acids                                                             

            26.2     Waxes Are High-Molecular Weight Esters                                                                               

            26.3     Fats and Oils                                                                           

26.4     Phospholipids and Sphingolipids are the Components of Membranes                            

            26.5     Prostaglandins  Regulate Physiological Responses                                                                    

            26.6     Terpenes Contain Carbon Atoms in Multiples of Five                                                   

            26.7     Vitamin A Is a Terpene                                                                                    

            26.8     How Terpenes Are Biosynthesized                                                                   

            26.9     Steroids Are Chemical Messengers                                                                                          

            26.10   How Nature Synthesizes Cholesterol                                        

            26.11   Synthetic Steroids                                                                                

CHAPTER 27.  NUCLEOSIDES, NUCLEOTIDES, AND NUCLEIC ACIDS                           

            27.1     Nucleosides and Nucleotides                                       

            27.2     Other Important Nucleotides

            27.3     Nucleic Acids Are Composed of Nucleotide Subunits  

            27.4     DNA Is Stable but RNA Is Easily Cleaved                                                      

            27.5     Biosynthesis of DNA Is Called Replication                                                       

            27.6     Biosynthesis of RNA Is Called Transcription                                                    

            27.7     There Are Three Kinds of RNA

            27.8     Biosynthesis of Proteins Is Called Translation                                                               

            27.9     Why DNA Contains Thymine Instead of Uracil                                                

            27.10   How the Base Sequence of DNA Is Determined                                                                      

            27.11   Polymerase Chain Reaction (PCR)                                                       

            27.12   Genetic Engineering                                                     

27.13   Laboratory Synthesis of DNA Strands                                     

PART IX: SPECIAL TOPICS IN ORGANIC CHEMISTRY

CHAPTER 28.  SYNTHETIC POLYMERS                                                           

            28.1     There Are Two Major Classes of Synthetic Polymers                           

            28.2     Chain-Growth Polymers                                                                      

                                    Radical Polymerization                                                 

                                    Branching of the Polymer Chain                                               

                                    Cationic Polymerization                                                

                                    Anionic Polymerization                                                 

            28.3     Stereochemistry of Polymerization.  Ziegler-Natta Catalysts      

            28.4     Polymerization of Dienes. The Manufacture of Rubber                          

            28.5     Copolymers                                                                                         

            28.6     Step-Growth Polymers                                                            

            28.7     Physical Properties of Polymers                                                           

CHAPTER 29.  PERICYCLIC REACTIONS                                                                    

            29.1     There Are Three Kinds of Pericyclic Reations                                      

            29.2     Molecular Orbitals and Orbital Symmetry                                                                     

            29.3     Electrocyclic Reactions

            29.4     Cycloaddition Reactions                                  

29.5     Sigmatropic Rearrangements    

Migration of Hydrogen

Migration of Carbon                                                                            

29.6     Pericyclic Rections in  Biological Systems

Biological Cycloaddition Reactions

A Biological Reaction Involving an Electrocyclic Reaction and a Sigmatropic

Rearrangement                                                            

            29.7     Summary of the Selection Rules for Pericyclic Reactions                                                           

CHAPTER 30. THE ORGANIC CHEMISTRY OF DRUGS

   DISCOVERY AND DESIGN                                                                   

            30.1     Naming Drugs                                     

            30.2     Lead Compounds                                                                    

            30.3     Molecular Modification

            30.4     Random Screening                   

            30.5     Serendipity in Drug Development                                                                                 

            30.6     Receptors                                                                    

            30.7     Drugs as Enzyme Inhibitors                                          

            30.8     Designing a Suicide Substrate

            30.9     Quantitative Structure-Activity Relationships (QSARs)                                     

            30.10   Molecular Modeling                                                     

            30.11   Combinatorial Organic Synthesis                                                          

            30.12   Antiviral Drugs                                                             

            30.13   Economics of Drugs: Governmental Regulations