Arene Chemistry E-Book

Jacques Mortier

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1729

Veröffentlichungsjahr: 2015

Beschreibung

Organized to enable students and synthetic chemists to understand and expand on aromatic reactions covered in foundation courses, the book offers a thorough and accessible mechanistic explanation of aromatic reactions involving arene compounds. * Surveys methods used for preparing arene compounds and their transformations * Connects reactivity and methodology with mechanism * Helps readers apply aromatic reactions in a practical context by designing syntheses * Provides essential information about techniques used to determine reaction mechanisms

Leseprobe

TABLE OF CONTENTS

COVER

TITLE PAGE

LIST OF CONTRIBUTORS

PREFACE

PART I: ELECTROPHILIC AROMATIC SUBSTITUTION

1 ELECTROPHILIC AROMATIC SUBSTITUTION: MECHANISM

1.1 INTRODUCTION

1.2 GENERAL ASPECTS

1.3 ELECTROPHILES

1.4 ARENE NUCLEOPHILES

1.5 π-COMPLEX INTERMEDIATES

1.6 σ-COMPLEX OR WHELAND INTERMEDIATES

1.7 SUMMARY AND OUTLOOK

ABBREVIATIONS

REFERENCES

2 FRIEDEL–CRAFTS ALKYLATION OF ARENES IN TOTAL SYNTHESIS

2.1 INTRODUCTION

2.2 TOTAL SYNTHESIS INVOLVING INTERMOLECULAR FC ALKYLATIONS

2.3 TOTAL SYNTHESIS INVOLVING INTRAMOLECULAR FC ALKYLATIONS

2.4 TOTAL SYNTHESIS THROUGH TANDEM AND CASCADE PROCESSES INVOLVING FC REACTIONS

2.5 TOTAL SYNTHESIS INVOLVING

ipso

-FC REACTIONS

2.6 SUMMARY AND OUTLOOK

2.7 ACKNOWLEDGMENT

ABBREVIATIONS

REFERENCES

3 CATALYTIC FRIEDEL–CRAFTS ACYLATION REACTIONS

3.1 INTRODUCTION AND HISTORICAL BACKGROUND

3.2 CATALYTIC HOMOGENEOUS ACYLATIONS

3.3 CATALYTIC HETEROGENEOUS ACYLATIONS

3.4 DIRECT PHENOL ACYLATION

3.5 SUMMARY AND OUTLOOK

ABBREVIATIONS

REFERENCES

4 THE USE OF QUANTUM CHEMISTRY FOR MECHANISTIC ANALYSES OF S

E

Ar REACTIONS

4.1 INTRODUCTION

4.2 THE S

E

Ar MECHANISM: QUANTUM CHEMICAL CHARACTERIZATION IN GAS PHASE AND SOLUTION

4.3 PREDICTION OF RELATIVE REACTIVITY AND REGIOSELECTIVITY BASED ON QUANTUM CHEMICAL DESCRIPTORS

4.4 QUANTUM CHEMICAL REACTIVITY PREDICTION BASED ON MODELING OF TRANSITION STATES AND INTERMEDIATES

4.5 SUMMARY AND CONCLUSIONS

ABBREVIATIONS

REFERENCES

5 CATALYTIC ENANTIOSELECTIVE ELECTROPHILIC AROMATIC SUBSTITUTIONS

5.1 INTRODUCTION AND HISTORICAL BACKGROUND

5.2 METAL-CATALYZED AFCA OF AROMATIC HYDROCARBONS

5.3 ORGANOCATALYZED AFCA OF AROMATIC HYDROCARBONS

5.4 MERGING ASYMMETRIC METAL AND ORGANOCATALYSIS IN FRIEDEL–CRAFTS ALKYLATIONS

5.5 SUMMARY AND OUTLOOK

ABBREVIATIONS

REFERENCES

PART II: NUCLEOPHILIC AROMATIC SUBSTITUTION

6 NUCLEOPHILIC AROMATIC SUBSTITUTION

6.1 INTRODUCTION

6.2 THE S

N

Ar MECHANISM

6.3 MEISENHEIMER ADDUCTS

6.4 THE S

N

1 MECHANISM

6.5 SYNTHETIC APPLICATIONS

ABBREVIATIONS

REFERENCES

7 THEORETICAL AND EXPERIMENTAL METHODS FOR THE ANALYSIS OF REACTION MECHANISMS IN S

N

Ar PROCESSES

7.1 INTRODUCTION

7.2 CONCEPTUAL DFT: GLOBAL, REGIONAL, AND NONLOCAL REACTIVITY INDICES

7.3 PRACTICAL APPLICATIONS OF CONCEPTUAL DFT DESCRIPTORS

7.4 S

N

Ar REACTION MECHANISM

7.5 INTEGRATED EXPERIMENTAL AND THEORETICAL MODELS

7.6 SOLVENT EFFECTS IN CONVENTIONAL SOLVENTS AND IONIC LIQUIDS

7.7 SUMMARY AND OUTLOOK

ABBREVIATIONS

REFERENCES

8 ASYMMETRIC NUCLEOPHILIC AROMATIC SUBSTITUTION

8.1 INTRODUCTION

8.2 AUXILIARY- AND SUBSTRATE-CONTROLLED ASYMMETRIC NUCLEOPHILIC AROMATIC SUBSTITUTION

8.3 CHIRAL CATALYZED ASYMMETRIC NUCLEOPHILIC AROMATIC SUBSTITUTION

8.4 ABSOLUTE ASYMMETRIC NUCLEOPHILIC AROMATIC SUBSTITUTION

8.5 SUMMARY AND OUTLOOK

ABBREVIATIONS

REFERENCES

9 HOMOLYTIC AROMATIC SUBSTITUTION

9.1 INTRODUCTION: SCOPE AND LIMITATIONS

9.2 RADICALS GENERATED BY HOMOLYTIC CLEAVAGE PROCESSES: THERMOLYSIS AND PHOTOLYSIS

9.3 REACTIONS MEDIATED BY TIN AND SILICON HYDRIDES

9.4 RADICALS GENERATED BY ET: REDOX REACTIONS

9.5 SUMMARY AND OUTLOOK

ABBREVIATIONS

REFERENCES

10 RADICAL-NUCLEOPHILIC AROMATIC SUBSTITUTION

10.1 INTRODUCTION: SCOPE AND LIMITATIONS—BACKGROUND

10.2 MECHANISTIC CONSIDERATIONS

10.3 INTERMOLECULAR S

RN

1 REACTIONS

10.4 INTRAMOLECULAR S

RN

1 REACTIONS