Organolithiums

Selectivity for Synthesis

By: J Clayden

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Paperback | 12 July 2002

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This volume, number 23 in the "Tetrahedron Organic Chemistry" series, presents organolithium chemistry from the perspective of a synthetic organic chemist, drawing from the synthetic literature to present a unified overview of how organolithiums can be used to make molecules. The development of methods for the regioselective synthesis of organolithiums has replaced their image of indiscriminate high reactivity with one of controllable and subtle selectivity. Organolithium chemistry has a central role in the selective construction of C-C bonds in both simple and complex molecules, and for example has arguably overtaken aromatic electrophilic substitution as the most powerful method for regioselective functionalisation of aromatic rings. The twin themes of reactivity and selectivity run through the book, which reviews the ways by which organolithiums may be formed and the ways in which they react. Topics include advances in directed metallation, reductive lithiation and organolithium cyclisation reactions, along with a discussion of organolithium stereochemistry and the role played by ligands such as (-)-sparteine.

Industry Reviews

"Organolithiums: Selectivity for Synthesis" is recommended for every chemist who wishes to become thoroughly acquainted with the potential of organolithium chemistry. Jonathan Clayden has succeeded in conveying this knowledge with succinct commentaries supported by appropriate examples. --ORGANIC CHEMISTRY, 2005

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Published: 1st November 2006

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Foreword	p. xi
Acknowledgements	p. xiii
Abbreviations	p. xv
Introduction	p. 1
Scope and overview	p. 1
Organolithiums in solution	p. 2
References	p. 7
Regioselective Synthesis of Organolithiums by Deprotonation	p. 9
General points	p. 9
Lithiation [alpha] to heteroatoms	p. 10
Lithiation [alpha] to oxygen	p. 12
Lithiation [alpha] to nitrogen	p. 14
Amides	p. 15
Benzotriazoles and other 5-membered heterocycles	p. 20
Formamidines	p. 20
Nitrosoamines	p. 21
Imines	p. 22
Isocyanides	p. 23
Lithiation of trigonal C-H [alpha] to nitrogen	p. 23
N-oxides and amine-boron complexes	p. 23
Lithiation [alpha] to sulfur	p. 24
Lithiation [alpha] to silicon	p. 26
Lithiation at unfunctionalised allylic positions	p. 26
Ortholithiation	p. 28
Introduction: mechanism	p. 28
Classes of directing group	p. 34
N+O class	p. 36
Secondary and tertiary amides	p. 36
[alpha]-Amino alkoxides	p. 41
Oxazolines	p. 43
O-Carbamates	p. 44
Anilides and N-aryl carbamates	p. 45
S+O class	p. 46
N class	p. 50
Aminomethyl groups	p. 50
Anilines and isocyanides	p. 51
Imines, nitriles, hydrazones and nitrogen heterocycles	p. 51
O class	p. 53
Ethers and alkoxides	p. 53
Ketones, esters and carboxylates	p. 56
X class	p. 58
Ortholithiation of aromatic heterocycles	p. 59
Electron-deficient heterocycles	p. 59
Electron-rich heterocycles	p. 70
Lithiation of metal-arene complexes	p. 71
Chromium-arene complexes	p. 71
Ferrocenes	p. 72
Lateral lithiation	p. 73
Mechanism and regioselectivity	p. 73
Classes of directing group	p. 75
Secondary and tertiary amides	p. 75
Nitriles	p. 77
Oxazolines, imidazolines and tetrazoles	p. 77
Carboxylates	p. 77
Carboxylic esters	p. 78
Ketones	p. 78
Aldehydes protected as [alpha]-amino alkoxides	p. 79
Alcohols and phenols (cresols) and their derivatives	p. 79
Sulfur-based functional groups	p. 81
Aniline and aminoalkylbenzene derivatives	p. 82
Halogens	p. 83
Lateral lithiation of heterocycles	p. 83
Remote lithiation, and [beta]-lithiation of non-aromatic compounds	p. 86
Superbases	p. 87
Cooperation, competition and regioselectivity	p. 90
References	p. 96
Regioselective Synthesis of Organolithiums by X-Li Exchange	p. 111
Halogen-lithium exchange	p. 111
Reactivity	p. 111
Mechanism	p. 118
Synthesis of aryllithiums	p. 124
Synthesis of heteroaryllithiums	p. 127
Synthesis of vinyllithiums	p. 132
Synthesis of alkyllithiums	p. 134
Diastereoselective halogen-lithium exchange	p. 135
Tin-lithium exchange	p. 136
Chalcogen-lithium exchange	p. 139
Selenium-lithium exchange	p. 139
Tellurium-lithium exchange	p. 141
Sulfur-lithium exchange	p. 141
Phosphorus-lithium exchange	p. 142
References	p. 142
Regioselective Synthesis of Organolithiums by C-X Reduction	p. 149
Reductive lithiation of alkyl and aryl halides	p. 149
Reductive lithiation with lithium metal	p. 149
Reductive lithiation promoted by arenes	p. 150
Reductive lithiation of C-O bonds	p. 154
Reductive lithiation of C-N bonds	p. 158
Reductive lithiation of C-S bonds	p. 159
Reduction of sulfides	p. 159
Reduction of sulfones	p. 164
Reductive lithiation of C-C bonds and [pi]-bonds	p. 165
References	p. 165
Stereoselective and Stereospecific Synthesis of Organolithiums	p. 169
Configurational stability of organolithiums	p. 169
Determining configurational stability	p. 169
Unfunctionalised organolithiums	p. 175
Secondary organolithiums	p. 175
Primary organolithiums	p. 175
Solvent effects	p. 176
Cyclopropyllithiums	p. 176
Organolithiums [alpha] to oxygen	p. 178
Simple acyclic [alpha]-alkoxy organolithiums	p. 178
Cyclic [alpha]-alkoxy organolithiums	p. 180
Oxiranyllithiums	p. 183
Allylic and benzylic [alpha]-alkoxy organolithiums	p. 184
Organolithiums [alpha] to nitrogen	p. 186
Cyclic [alpha]-amino organolithiums: 3-membered rings	p. 186
Pyrrolidinyllithiums and piperidinyllithiums: 5- and 6-membered rings	p. 188
Lithiated formamidines	p. 191
Acyclic [alpha]-amino organolithiums	p. 192
Benzylic and allylic [alpha]-amino organolithiums	p. 193
Crystallographic and theoretical data	p. 195
Organolithiums [alpha] to halogens	p. 197
Organolithiums [alpha] to sulfur	p. 199
Lithiated sulfides	p. 199
Lithiated thiocarbamates	p. 202
Lithiated sulfones	p. 202
Mechanism of racemisation	p. 204
Organolithiums [alpha] to selenium	p. 205
Organolithiums [alpha] to phosphorus	p. 207
Organolithiums [alpha] to silicon	p. 207
Benzyllithiums	p. 208
Secondary benzyllithiums	p. 208
Tertiary benzyllithiums	p. 211
Vinyllithiums	p. 212
Summary	p. 213
Stereospecific synthesis of organolithiums by X-Li exchange	p. 214
Tin-lithium exchange	p. 214
Vinylstannanes	p. 214
[alpha]-Heterosubstituted stannanes	p. 214
Non-heterosubstituted stannanes	p. 216
Halogen-lithium exchange	p. 222
Selenium-lithium exchange	p. 222
Sulfur-lithium exchange	p. 223
Other metal-lithium exchanges	p. 223
Stereospecific deprotonation	p. 223
Diastereoselective deprotonation	p. 224
Diastereoselective lateral lithiation	p. 224
Diastereoselective ortholithiation	p. 225
Enantioselective deprotonation	p. 226
References	p. 235
Stereospecific and Stereoselective Substitution Reactions of Organolithiums	p. 241
Stereospecific reactions of organolithium compounds	p. 241
Introduction	p. 241
Vinyllithiums	p. 242
Non-stabilised alkyllithiums	p. 242
The general rule: retention (S[subscript E]2ret)	p. 242
The exception - alkylation of lithiated N-alkyl pyrrolidines and piperidines: inversion (S[subscript E]2inv)	p. 246
Rearrangements ([1,2] and [2,3], except Brook rearrangements) of unstabilised organolithiums: inversion (S[subscript E]2inv)	p. 247
Stabilised alkyllithiums: retention (S[subscript E]2ret) or inversion (S[subscript E]2inv)?	p. 249
Benzyllithiums	p. 249
Allyllithiums	p. 256
Rearrangements of stabilised organolithiums	p. 257
Stereoselective substitution in the presence of chiral ligands	p. 258
Introduction: Mechanisms	p. 258
Chiral ligands	p. 258
Enantioselective deprotonation	p. 260
Enantioselective substitution	p. 260
Configurational stability, stereospecificity, and dynamic resolutions	p. 261
Dynamic thermodynamic resolution	p. 262
Dynamic kinetic resolution	p. 268
Summary: mechanisms of asymmetric functionalisation with (-)-sparteine	p. 268
References	p. 269
Regio- and Stereoselective Addition Reactions of Organolithiums	p. 273
Intermolecular addition to [pi] bonds: Carbolithiation	p. 273
Carbolithiation of simple alkenes	p. 273
Carbolithiation of conjugated alkenes and alkynes	p. 274
Carbolithiation of functionalised alkenes	p. 276
Enantioselective carbolithiation	p. 280
Intramolecular addition and substitution reactions: anionic cyclisation	p. 282
Anionic cyclisations onto carbonyl compounds and derivatives	p. 282
Cyclisations of aryllithiums - Parham cyclisations	p. 282
Cyclisations of alkenyllithiums	p. 284
Cyclisations of alkyllithiums	p. 286
Cyclisations of alkynyllithiums	p. 287
Anionic cyclisations onto epoxides	p. 288
Anionic cyclisations onto alkyl halides and similar compounds	p. 290
Anionic cyclisations onto alkenes and alkynes	p. 293
Cyclisation onto activated alkenes	p. 293
Cyclisation onto unactivated alkenes	p. 294
Cyclopentanes	p. 301
Cascade reactions	p. 308
Tetrahydrofurans	p. 310
Pyrrolidines	p. 312
Tetrahydrothiophenes	p. 314
Stereoselectivity and mechanism	p. 314
Anionic cyclisation onto allenes	p. 321
Anionic cyclisation onto alkynes	p. 321
Anionic cyclisation onto aromatic rings	p. 327
References	p. 329
Organolithium Rearrangements	p. 337
Shapiro Reaction	p. 337
Brook Rearrangements	p. 340
[1,2]-Brook Rearrangements	p. 342
[1,3]-Brook Rearrangements	p. 344
[1,4]-Brook Rearrangements	p. 344
[1,4]-Retro-Brook rearrangements	p. 345
[1,2]-Wittig Rearrangements	p. 346
Mechanism and scope	p. 346
Stereospecificity	p. 348
[1,2]-Wittig rearrangements in synthesis	p. 350
[2,3]-Wittig Rearrangements	p. 351
Regioselectivity	p. 352
Diastereoselectivity	p. 354
Double bond geometry	p. 354
Syn/anti relative stereochemistry	p. 355
Stereospecificity and enantioselectivity	p. 355
Stereospecific rearrangements of chiral allyl ethers	p. 355
Stereoselective rearrangements with chiral auxiliaries	p. 357
Stereospecific rearrangements of chiral organolithiums	p. 357
[2,3]-Aza-Wittig rearrangements	p. 359
References	p. 360
Organolithiums in Synthesis	p. 365
Ochratoxin: ortholithiation and anionic Fries rearrangement	p. 365
Corydalic acid methyl ester: lateral lithiation	p. 366
Fredericamycin A: ortho, lateral and [alpha]-lithiation	p. 367
([plus or minus])-Atpenin B: metallation of an aromatic heterocycle	p. 369
Flurbiprofen: metallation with LiCKOR superbases	p. 370
California Red Scale Pheromone: [alpha]- and reductive lithiation	p. 371
C1-C9 of the Bryostatins: diastereoselective bromine-lithium exchange	p. 372
(S)-1-Methyldodecyl acetate, a Drosophila pheromone: (-)-sparteine assisted enantioselective lithiation	p. 373
(-)-Paroxetine: (-)-sparteine-promoted asymmetric lithiation and substitution	p. 374
References	p. 375
Index	p. 377
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Organolithiums

Selectivity for Synthesis

At a Glance

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Industry Reviews

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