Pericyclic Reactions / Edition 2

by Ian Fleming

Overview

Pericyclic reactions constitute a major strand of organic chemistry, including such commercially important synthetic reactions as the Diels-Alder reaction. Reactions such as these are characterised by their predictable stereochemistry and cyclic transition structures. This primer reviews these reactions in order to explain their theoretical basis via correlation diagrams. It also shows students how to recognize the different types of pericyclic reaction, their mechanisms, and their applications to organic synthesis.

The text is part of the renowned Oxford Chemistry Primer series, which provides focused introductions to a range of important topics in chemistry. The series has been refreshed and updated to suit the needs of today's students and instructors. The rigorous, yet accessible, the texts include cutting-edge examples and relevant applications.

Pedagogical features provided in the primers—including questions at the end of every chapter, diagrams, margin notes, suggestions for further reading, and an expansive glossary—encourage active learning and promote understanding.

Product Details

ISBN-13:	9780199680900
Publisher:	Oxford University Press
Publication date:	06/02/2015
Series:	Oxford Chemistry Primers
Edition description:	New Edition
Pages:	128
Product dimensions:	5.80(w) x 8.20(h) x 0.40(d)

About the Author

Ian Fleming is Professor Emeritus of Chemistry at the University of Cambridge. He studied at Pembroke College, Cambridge, obtaining his PhD in 1962 in the University Chemical Laboratory supervised by Dr John Harley-Mason. After a year of independent research as a Research Fellow in Pembroke College, he spent a postdoctoral year at Harvard (1963-1964) with Professor R. B. Woodward, before returning to Cambridge, where he was successively Assistant Director of Research, Lecturer, Reader, and Professor of Organic Chemistry. In 1993 he was elected as a Fellow of the Royal Society in recognition of his work on the application of organosilicon chemistry to solving problems of regiocontrol and stereocontrol in organic synthesis. He formally retired from research in 2002, but remains active in writing and teaching.

Table of Contents

Preface v

Chapter 1 The nature of pericyclic reactions 1

1.1 Introduction 1

1.2 Ionic, radical, and pericyclic reactions 1

1.3 The four classes of pericyclic reactions 3

1.4 Cycloadditions 3

1.5 Electrocyciic reactions 4

1.6 Sigmatropic rearrangements 5

1.7 Group transfer reactions 6

1.8 Further reading 7

1.9 Exercises 7

Chapter 2 Cycloaddition reactions 8

2.1 Introduction 8

2.2 Diels-Alder reactions 8

2.3 1,3-Dipolar cycloadditions 11

2.4 [4 + 2] Cycloadditions of cations and anions 14

2.5 Cycloadditions involving more than six electrons 17

2.6 Allowed and forbidden reactions 18

2.7 Photochemical cycloadditions 19

2.8 The stereochemistry of cycloadditions 19

2.9 Regie-selectivity of cycloadditions 25

2.10 Intramolecular cycloadditions 27

2.11 Not all cycloadditions are pericyclic 28

2.12 Cheletiopic reactions 30

2.13 Further reading 31

2.14 Problems 33

2.15 Summary 34

Chapter 3 The Woodward-Hoffmann rules and molecular orbitals 35

3.1 Introduction 35

3.2 Evidence for the concertedness of bond making and breaking 35

3.3 The aromatic transition structure 37

3.4 Frontier orbitals 37

3.5 Correlation diagrams 39

3.6 The Woodward-Hoffmann rules applied to cycloadditions 44

3.7 Some anomalous [2 + 2] cycloadditions 50

3.8 Secondary effects 53

3.9 Further reading 60

3.10 Problems 61

3.11 Summary 63

Chapter 4 Electrocyclic reactions 64

4.1 Introduction 64

4.2 Neutral polyenes 64

4.3 Ionic conjugated systems 64

4.4 Stereochemistry 67

4.5 The Woodward-Hoffmann rules applied to thermal electrocyclic reactions 69

4.6 Photochemical electrocyclic reactions 76

4.7 Further reading 78

4.8 Problems 78

4.9 Summary 80

Chapter 5 Sigmatropic rearrangements 82

5.1 Introduction 82

5.2 [l,n] Rearrangements-suprafacial and antarafacial 82

5.3 [m, n] Rearrangements 90

5.4 Further reading 95

5.5 Problems 95

5.6 Summary 96

Chapter 6 Group transfer reactions 98

6.1 Introduction 98

6.2 Ene reactions 98

6.3 Retro ene reactions and other thermal eliminations 101

6.4 Dumide and related reductions 102

6.5 1,4-Elimination of hydrogen 103

6.6 Further reading 103

6.7 Problems 104

6.8 Summary 104

Exercises 105

Answers to Problems 109

Glossary 113

Index 117