Page 10 - Arrow Pushing in Inorganic Chemistry A Logical Approach to the Chemistry of the Main Group Elements

CONTENTS
viii
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5B.13 The Mitsunobu Reaction 188
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5B.14 The Vilsmeier–Haack Reaction 191
5B.15 SbF and Superacids 193
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5B.16 Bismuth in Organic Synthesis: Green Chemistry 195
5B.17 Summary 200
Further Reading 200

6. Group 16 Elements: The Chalcogens 202
6.1 The Divalent State: Focus on Sulfur 204
6.2 The Divalent State: Hydrogen Peroxide 205
6.3 S Cl and SCl 209
2 2 2
6.4 Nucleophilic Breakdown of Cyclopolysulfur Rings 211
6.5 Cyclooctachalcogen Ring Formation 213
6.6 Higher-Valent States: Oxides and Oxoacids 215
6.7 Sulfur Oxochlorides 219
6.8 Ozone 222
6.9 Swern and Related Oxidations 226
6.10 Sulfur Ylides and Sulfur-Stabilized Carbanions 228
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6.11 Hydrolysis of S F : A Mechanistic Puzzle 231
2 2
6.12 Higher-Valent Sulfur Fluorides 234
6.13 Martin Sulfurane 236
6.14 Lawesson’s Reagent 238
6.15 Sulfur Nitrides 240
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6.16 Selenium-Mediated Oxidations 243
6.17 Higher-Valent Tellurium: A Mechanistic Puzzle 247
6.18 Summary 250
Further Reading 251

7. The Halogens 252
7.1 Some Notes on Elemental Halogens 254
7.2 Alkali-Induced Disproportionation of Molecular Halogens 258
7.3 Acid-Induced Comproportionation of Halate and Halide 260
7.4 Hypofluorous Acid, HOF 261
7.5 Electrophilic Fluorinating Agents: N-Fluoro Compounds 264
7.6 Oxoacids and Oxoanions 268
7.7 Heptavalent Chlorine 271
7.8 Interhalogen Compounds 275
7.9 ∗ Halogens in Organic Synthesis: Some Classical Reactions 276
7.10 An Introduction to Higher-Valent Organoiodine Compounds 283
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7.11 -Iodanes 284
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7.12 -Iodanes: IBX and Dess–Martin Periodinane 288