The Wolff-Kishner Reduction and Related Reactions: Discovery and Development offers a detailed discussion of this reaction, its discoverers, and its development since its discovery. Derivative name reactions—including the Wharton and Shapiro reactions—are also discussed. The book is illustrated with examples from literature and corresponding references to the primary literature to aid further reading. It provides a comprehensive review of the century of chemistry that allows the reader to follow the development of this important synthetic reaction. In addition, it provides biographical details on the chemists who discovered and developed the reaction, thus adding a human dimension to the discussion.
Author(s): David E. Lewis
Edition: 1
Publisher: Elsevier
Year: 2019
Language: English
Pages: 234
Cover......Page 1
The Wolff-Kishner
Reduction and Related
Reactions:
Discovery and Development......Page 3
Copyright......Page 4
Dedication......Page 5
Preface......Page 6
Acknowledgments......Page 8
Nikolai Matveevich Kizhner: A truly eventful life......Page 9
Kizhners graduate research at Moscow......Page 14
Professor at Tomsk......Page 17
The Kizhner cyclopropane synthesis......Page 21
Kizhner, campus politics and the revolution of 1905......Page 23
Kizhner in Soviet Moscow......Page 35
Ludwig Wolff......Page 39
The Wolff rearrangement......Page 42
References......Page 44
1911-1913: Kizhner's initial disclosures of the reaction......Page 51
1911: Wolff's version of the reaction......Page 58
Settling the question of priority......Page 60
References......Page 63
The ionic mechanism......Page 65
Free radical intermediates in the Wolff-Kishner reduction?......Page 68
Free radical intermediates? maybe not......Page 69
Free radical intermediates? then again, maybe yes......Page 70
Pyrazolines and N-alkylhydrazones......Page 72
Side reactions in the Wolff-Kishner reduction......Page 73
Early exploration of the scope and limitations of the reaction......Page 76
Higher terpenoids and steroids......Page 78
Haloazines: Reactions of halogenated pyridines, quinolines and purines with hydrazine......Page 86
Alkaloids......Page 88
Other alicyclic compounds......Page 90
Polycyclic aromatic hydrocarbons and their derivatives......Page 91
References......Page 94
Introduction......Page 99
The Huang-Minlon modification of the Wolff-Kishner reduction......Page 100
The discoverer of the reaction......Page 103
Steroids and santonins......Page 104
Steroids......Page 106
Representative applications of the Huang-Minlon method......Page 108
Aromatic aldehydes and ketones......Page 110
Bile acids, steroids and triterpenes......Page 113
Other alicyclic systems......Page 118
Nitrogen heterocycles......Page 120
Sulfur heterocycles......Page 122
Alkaloids and cyclic amines......Page 125
Limitations of the Wolff-Kishner reduction......Page 129
A final word......Page 130
References......Page 135
Introduction......Page 141
Effects of steric hindrance on the Wolff-Kishner reaction......Page 142
The Barton modification......Page 145
The Nagata modification......Page 148
The Henbest modification......Page 151
The Cram modification......Page 154
What about not using a base at all? Deoxygenation by reduction of sulfonylhydrazones......Page 156
The Caglioti modification......Page 157
The Hutchins modification (40)......Page 159
Tosylhydrazones and strong bases: Alkenes and carbenes from carbonyl compounds......Page 164
Metal Alkyls: the Shapiro reaction (56, 59)......Page 167
Metal alkoxides: The Bamford-Stevens reaction (57)......Page 168
References......Page 171
Reduction of α-amino-, α-alkoxy- and α-hydroxyketones......Page 176
Reduction of α-halo- and α-tosyloxyketones......Page 183
Systems resistant to the Kishner reduction-elimination......Page 185
Kishner reduction-elimination reactions of epoxyketones......Page 186
Acid-catalyzed reduction of epoxyketones by hydrazine: The Wharton reaction......Page 188
The reduction of 2-acylaziridines to allylamines by hydrazine: The aza-Wharton reaction (33)......Page 190
The reaction of epoxyketones with tosylhydrazine: The Eschenmoser fragmentation......Page 192
References......Page 195
Further reading......Page 197
Natural products......Page 198
Cyclophanes......Page 199
Compounds for medicine......Page 200
Compounds for materials science and technology......Page 206
End-stage reactions in multistep syntheses......Page 209
The Barton modification......Page 212
The Nagata modification......Page 213
The Wharton and Aza-Wharton reactions......Page 214
The Eschenmoser fragmentation......Page 215
The Shapiro reaction......Page 218
References......Page 221
Further reading......Page 224
B......Page 225
C......Page 226
E......Page 227
H......Page 228
K......Page 229
N......Page 230
S......Page 231
W......Page 232
Z......Page 233
Back Cover......Page 234
