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Organolithiums : Selectivity for Synthesis - J Clayden

Organolithiums

Selectivity for Synthesis

By: J Clayden

Paperback Published: 26th July 2002
ISBN: 9780080432618
Number Of Pages: 383

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This book, Volume 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 (compounds in which there is a clear carbon-lithium bond) can be used to make molecules.

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.

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

Forewordp. xi
Acknowledgementsp. xiii
Abbreviationsp. xv
Introductionp. 1
Scope and overviewp. 1
Organolithiums in solutionp. 2
Referencesp. 7
Regioselective Synthesis of Organolithiums by Deprotonationp. 9
General pointsp. 9
Lithiation [alpha] to heteroatomsp. 10
Lithiation [alpha] to oxygenp. 12
Lithiation [alpha] to nitrogenp. 14
Amidesp. 15
Benzotriazoles and other 5-membered heterocyclesp. 20
Formamidinesp. 20
Nitrosoaminesp. 21
Iminesp. 22
Isocyanidesp. 23
Lithiation of trigonal C-H [alpha] to nitrogenp. 23
N-oxides and amine-boron complexesp. 23
Lithiation [alpha] to sulfurp. 24
Lithiation [alpha] to siliconp. 26
Lithiation at unfunctionalised allylic positionsp. 26
Ortholithiationp. 28
Introduction: mechanismp. 28
Classes of directing groupp. 34
N+O classp. 36
Secondary and tertiary amidesp. 36
[alpha]-Amino alkoxidesp. 41
Oxazolinesp. 43
O-Carbamatesp. 44
Anilides and N-aryl carbamatesp. 45
S+O classp. 46
N classp. 50
Aminomethyl groupsp. 50
Anilines and isocyanidesp. 51
Imines, nitriles, hydrazones and nitrogen heterocyclesp. 51
O classp. 53
Ethers and alkoxidesp. 53
Ketones, esters and carboxylatesp. 56
X classp. 58
Ortholithiation of aromatic heterocyclesp. 59
Electron-deficient heterocyclesp. 59
Electron-rich heterocyclesp. 70
Lithiation of metal-arene complexesp. 71
Chromium-arene complexesp. 71
Ferrocenesp. 72
Lateral lithiationp. 73
Mechanism and regioselectivityp. 73
Classes of directing groupp. 75
Secondary and tertiary amidesp. 75
Nitrilesp. 77
Oxazolines, imidazolines and tetrazolesp. 77
Carboxylatesp. 77
Carboxylic estersp. 78
Ketonesp. 78
Aldehydes protected as [alpha]-amino alkoxidesp. 79
Alcohols and phenols (cresols) and their derivativesp. 79
Sulfur-based functional groupsp. 81
Aniline and aminoalkylbenzene derivativesp. 82
Halogensp. 83
Lateral lithiation of heterocyclesp. 83
Remote lithiation, and [beta]-lithiation of non-aromatic compoundsp. 86
Superbasesp. 87
Cooperation, competition and regioselectivityp. 90
Referencesp. 96
Regioselective Synthesis of Organolithiums by X-Li Exchangep. 111
Halogen-lithium exchangep. 111
Reactivityp. 111
Mechanismp. 118
Synthesis of aryllithiumsp. 124
Synthesis of heteroaryllithiumsp. 127
Synthesis of vinyllithiumsp. 132
Synthesis of alkyllithiumsp. 134
Diastereoselective halogen-lithium exchangep. 135
Tin-lithium exchangep. 136
Chalcogen-lithium exchangep. 139
Selenium-lithium exchangep. 139
Tellurium-lithium exchangep. 141
Sulfur-lithium exchangep. 141
Phosphorus-lithium exchangep. 142
Referencesp. 142
Regioselective Synthesis of Organolithiums by C-X Reductionp. 149
Reductive lithiation of alkyl and aryl halidesp. 149
Reductive lithiation with lithium metalp. 149
Reductive lithiation promoted by arenesp. 150
Reductive lithiation of C-O bondsp. 154
Reductive lithiation of C-N bondsp. 158
Reductive lithiation of C-S bondsp. 159
Reduction of sulfidesp. 159
Reduction of sulfonesp. 164
Reductive lithiation of C-C bonds and [pi]-bondsp. 165
Referencesp. 165
Stereoselective and Stereospecific Synthesis of Organolithiumsp. 169
Configurational stability of organolithiumsp. 169
Determining configurational stabilityp. 169
Unfunctionalised organolithiumsp. 175
Secondary organolithiumsp. 175
Primary organolithiumsp. 175
Solvent effectsp. 176
Cyclopropyllithiumsp. 176
Organolithiums [alpha] to oxygenp. 178
Simple acyclic [alpha]-alkoxy organolithiumsp. 178
Cyclic [alpha]-alkoxy organolithiumsp. 180
Oxiranyllithiumsp. 183
Allylic and benzylic [alpha]-alkoxy organolithiumsp. 184
Organolithiums [alpha] to nitrogenp. 186
Cyclic [alpha]-amino organolithiums: 3-membered ringsp. 186
Pyrrolidinyllithiums and piperidinyllithiums: 5- and 6-membered ringsp. 188
Lithiated formamidinesp. 191
Acyclic [alpha]-amino organolithiumsp. 192
Benzylic and allylic [alpha]-amino organolithiumsp. 193
Crystallographic and theoretical datap. 195
Organolithiums [alpha] to halogensp. 197
Organolithiums [alpha] to sulfurp. 199
Lithiated sulfidesp. 199
Lithiated thiocarbamatesp. 202
Lithiated sulfonesp. 202
Mechanism of racemisationp. 204
Organolithiums [alpha] to seleniump. 205
Organolithiums [alpha] to phosphorusp. 207
Organolithiums [alpha] to siliconp. 207
Benzyllithiumsp. 208
Secondary benzyllithiumsp. 208
Tertiary benzyllithiumsp. 211
Vinyllithiumsp. 212
Summaryp. 213
Stereospecific synthesis of organolithiums by X-Li exchangep. 214
Tin-lithium exchangep. 214
Vinylstannanesp. 214
[alpha]-Heterosubstituted stannanesp. 214
Non-heterosubstituted stannanesp. 216
Halogen-lithium exchangep. 222
Selenium-lithium exchangep. 222
Sulfur-lithium exchangep. 223
Other metal-lithium exchangesp. 223
Stereospecific deprotonationp. 223
Diastereoselective deprotonationp. 224
Diastereoselective lateral lithiationp. 224
Diastereoselective ortholithiationp. 225
Enantioselective deprotonationp. 226
Referencesp. 235
Stereospecific and Stereoselective Substitution Reactions of Organolithiumsp. 241
Stereospecific reactions of organolithium compoundsp. 241
Introductionp. 241
Vinyllithiumsp. 242
Non-stabilised alkyllithiumsp. 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
Benzyllithiumsp. 249
Allyllithiumsp. 256
Rearrangements of stabilised organolithiumsp. 257
Stereoselective substitution in the presence of chiral ligandsp. 258
Introduction: Mechanismsp. 258
Chiral ligandsp. 258
Enantioselective deprotonationp. 260
Enantioselective substitutionp. 260
Configurational stability, stereospecificity, and dynamic resolutionsp. 261
Dynamic thermodynamic resolutionp. 262
Dynamic kinetic resolutionp. 268
Summary: mechanisms of asymmetric functionalisation with (-)-sparteinep. 268
Referencesp. 269
Regio- and Stereoselective Addition Reactions of Organolithiumsp. 273
Intermolecular addition to [pi] bonds: Carbolithiationp. 273
Carbolithiation of simple alkenesp. 273
Carbolithiation of conjugated alkenes and alkynesp. 274
Carbolithiation of functionalised alkenesp. 276
Enantioselective carbolithiationp. 280
Intramolecular addition and substitution reactions: anionic cyclisationp. 282
Anionic cyclisations onto carbonyl compounds and derivativesp. 282
Cyclisations of aryllithiums - Parham cyclisationsp. 282
Cyclisations of alkenyllithiumsp. 284
Cyclisations of alkyllithiumsp. 286
Cyclisations of alkynyllithiumsp. 287
Anionic cyclisations onto epoxidesp. 288
Anionic cyclisations onto alkyl halides and similar compoundsp. 290
Anionic cyclisations onto alkenes and alkynesp. 293
Cyclisation onto activated alkenesp. 293
Cyclisation onto unactivated alkenesp. 294
Cyclopentanesp. 301
Cascade reactionsp. 308
Tetrahydrofuransp. 310
Pyrrolidinesp. 312
Tetrahydrothiophenesp. 314
Stereoselectivity and mechanismp. 314
Anionic cyclisation onto allenesp. 321
Anionic cyclisation onto alkynesp. 321
Anionic cyclisation onto aromatic ringsp. 327
Referencesp. 329
Organolithium Rearrangementsp. 337
Shapiro Reactionp. 337
Brook Rearrangementsp. 340
[1,2]-Brook Rearrangementsp. 342
[1,3]-Brook Rearrangementsp. 344
[1,4]-Brook Rearrangementsp. 344
[1,4]-Retro-Brook rearrangementsp. 345
[1,2]-Wittig Rearrangementsp. 346
Mechanism and scopep. 346
Stereospecificityp. 348
[1,2]-Wittig rearrangements in synthesisp. 350
[2,3]-Wittig Rearrangementsp. 351
Regioselectivityp. 352
Diastereoselectivityp. 354
Double bond geometryp. 354
Syn/anti relative stereochemistryp. 355
Stereospecificity and enantioselectivityp. 355
Stereospecific rearrangements of chiral allyl ethersp. 355
Stereoselective rearrangements with chiral auxiliariesp. 357
Stereospecific rearrangements of chiral organolithiumsp. 357
[2,3]-Aza-Wittig rearrangementsp. 359
Referencesp. 360
Organolithiums in Synthesisp. 365
Ochratoxin: ortholithiation and anionic Fries rearrangementp. 365
Corydalic acid methyl ester: lateral lithiationp. 366
Fredericamycin A: ortho, lateral and [alpha]-lithiationp. 367
([plus or minus])-Atpenin B: metallation of an aromatic heterocyclep. 369
Flurbiprofen: metallation with LiCKOR superbasesp. 370
California Red Scale Pheromone: [alpha]- and reductive lithiationp. 371
C1-C9 of the Bryostatins: diastereoselective bromine-lithium exchangep. 372
(S)-1-Methyldodecyl acetate, a Drosophila pheromone: (-)-sparteine assisted enantioselective lithiationp. 373
(-)-Paroxetine: (-)-sparteine-promoted asymmetric lithiation and substitutionp. 374
Referencesp. 375
Indexp. 377
Table of Contents provided by Syndetics. All Rights Reserved.

ISBN: 9780080432618
ISBN-10: 0080432611
Series: Tetrahedron Organic Chemistry
Audience: General
Format: Paperback
Language: English
Number Of Pages: 383
Published: 26th July 2002
Publisher: Elsevier Science & Technology
Country of Publication: NL
Dimensions (cm): 24.03 x 16.71  x 1.6
Weight (kg): 0.8

Earn 347 Qantas Points
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