Modern organocopper chemistry / edited by Norbert Krause.

Format:

Book

Contributor:

Krause, Norbert.

Language:

English

Subjects (All):

Organocopper compounds--Handbooks, manuals, etc.

Organocopper compounds.

Genre:

Handbooks and manuals.

Physical Description:

xiv, 377 pages : illustrations ; 25 cm

Place of Publication:

Weinheim : Wiley-VCH, [2002]

Summary:

Organocopper compounds are now an integral part of every modern synthesis laboratory, allowing important stages of synthesis to be carried out in an elegant fashion. Yet a certain amount of experience is needed if they are to be used effectively. Non-experts in the field often have difficulty in choosing the most suitable reagent for a particular substrate and the prerequisites for the reaction. This manual, edited by Norbert Krause, answers such questions, since it contains all the useful tips and tricks on organocopper compounds - information gained from personal experience by the international team of authors. This allows those working in laboratories in both academia and industry to determine the optimal reagent for their needs using the substrates available for reaction and the desired products. The result is a more effective use of these synthesis tools in everyday laboratory practice.

Contents:

1 Structures and Reactivities of Organocopper Compounds / Johann T. B. H. Jastrzebski, Gerard van Koten 1

1.1.1 Historical Perspective 1

1.1.2 The Oxidation States of Copper 3

1.1.3 Thermal Stability and Bonding in Organocopper(I) Compounds 6

1.2 Homoleptic Organocopper Compounds Cu[subscript n]R[subscript n] 8

1.3 Heteroleptic Organocopper Compounds Cu[subscript n+m]R[subscript n]X[subscript m] 17

1.4 Organocuprates 26

1.4.1 Neutral Homoleptic and Heteroleptic Organocuprates 27

1.4.2 Anionic Homoleptic and Heteroleptic Organocuprates 32

1.4.3 Lower- and Higher-order Cyanocuprates 34

2 Transmetalation Reactions Producing Organocopper Reagents / Paul Knochel, Bodo Betzemeier 45

2.2 Transmetalation of Functionalized Organolithium and Organomagnesium Reagents 45

2.3 Transmetalation of Organoboron and Organoaluminium Reagents 51

2.4 Transmetalation of Functionalized Organozinc Reagents 54

2.4.1 Preparation of Organozinc Reagents 54

2.4.1.1 Preparation of Organozinc Halides 56

2.4.1.2 Preparation of Diorganozinc Reagents 59

2.4.2 Substitution Reactions with Copper-Zinc Reagents 62

2.4.3 Addition Reactions with Copper-Zinc Reagents 65

2.5 Transmetalation of Organotin, Organosulfur, and Organotellurium Reagents 67

2.6 Transmetalation of Organotitanium and Organomanganese Reagents 70

2.7 Transmetalation of Organozirconium and Organosamarium Reagents 71

3 Heteroatomcuprates and [alpha]-Heteroatomalkylcuprates in Organic Synthesis / R. Karl Dieter 79

3.2 Heteroatomcuprates 80

3.2.1 Group IVA Heteroatoms (Si, Ge, Sn) 80

3.2.1.1 Conjugate Addition Reactions 83

3.2.1.2 Silylcupration and Stannylcupration of Alkynes and Allenes 93

3.2.1.3 Substitution Reactions 102

3.2.2 Group VA and VIA Heteroatoms (N, O, P) 108

3.3 [alpha]-Heteroatomalkylcuprates 109

3.3.1 Group VI Heteroatoms (O, S, Se) 110

3.3.2 Group V Heteroatoms (N, P) and Silicon 114

3.3.3 [alpha]-Fluoroalkylcuprates and [alpha]-Fluoroalkenylcuprates 122

3.4 Non-transferable Heteroatom(alkyl)cuprates and [alpha]-Heteroatomalkylcuprates 123

3.4.1 Simple Residual Ligands 124

3.4.2 Chiral Ligands 127

4 Copper-mediated Addition and Substitution Reactions of Extended Multiple Bond Systems / Norbert Krause, Anja Hoffmann-Roder 145

4.2 Copper-mediated Addition Reactions to Extended Michael Acceptors 146

4.2.1 Acceptor-substituted Dienes 146

4.2.2 Acceptor-substituted Enynes 150

4.2.3 Acceptor-substituted Polyenynes 159

4.3 Copper-mediated Substitution Reactions of Extended Substrates 160

5 Copper(I)-mediated 1,2- and 1,4-Reductions / Bruce H. Lipshutz 167

5.2 More Recent Developments: Stoichiometric Copper Hydride Reagents 168

5.3 1,4-Reductions Catalytic in Cu(I) 174

5.4 1,2-Reductions Catalyzed by Copper Hydride 179

5.5 Heterogeneous CuH-Catalyzed Reductions 182

6 Copper-mediated Diastereoselective Conjugate Addition and Allylic Substitution Reactions / Bernhard Breit, Peter Demel 188

6.1 Conjugate Addition 188

6.1.1 Stereocontrol in Cyclic Derivatives 188

6.1.2 Stereocontrol in Acyclic Derivatives 192

6.1.2.1 [gamma]-Heteroatom-substituted Michael Acceptors 192

6.1.2.2 [gamma]-Alkyl-substituted [alpha],[beta]-Unsaturated Carbonyl Derivatives 198

6.1.2.3 [alpha],[beta]-Unsaturated Carbonyl Derivatives with Stereogenic Centers in Positions other than the [gamma]-Position 200

6.1.2.4 Directed Conjugate Addition Reactions 200

6.1.3 Auxiliary-bound Chiral Michael Acceptors and Auxiliary Chiral Metal Complexes 202

6.2 Allylic Substitution 210

7 Copper-catalyzed Enantioselective Conjugate Addition Reactions of Organozinc Reagents / Ben L. Feringa, Robert Naasz, Rosalinde Imbos, Leggy A. Arnold 224

7.2 Organozinc Reagents 227

7.3 Copper-catalyzed 1,4-Addition 229

7.3.1 Phosphoramidite-based Catalysts 229

7.3.2 Catalytic Cycle 233

7.3.3 Variation of Ligands 234

7.3.4 Cyclic Enones 239

7.3.5 2-Cyclopentenone 240

7.3.6 Acyclic Enones 242

7.4 Synthetic Applications 243

7.4.1 Tandem Conjugate Addition-Aldol Reactions 243

7.4.2 Kinetic Resolution of 2-Cyclohexenones 243

7.4.3 Sequential 1,4-Additions to 2,5-Cyclohexadienones 246

7.4.4 Lactones 250

7.4.5 Nitroalkenes 250

7.4.6 Annulation Methodology 252

8 Copper-Mediated Enantioselective Substitution Reactions / A. Sofia E. Karlstrom, Jan-Erling Backvall 259

8.2 Allylic Substitution 261

8.2.1 Allylic Substrates with Chiral Leaving Groups 262

8.2.2 Chiral Auxiliary that is Cleaved off after the Reaction 268

8.2.3 Catalytic Reactions with Chiral Ligands 272

8.3 Epoxides and Related Substrates 283

9 Copper-Mediated Synthesis of Natural and Unnatural Products / Yukiyasu Chounan, Yoshinori Yamamoto 289

9.1 Conjugate Addition 289

9.2 S[subscript N]2 Substitution 296

9.3 S[subscript N]2' Substitution 302

9.4 1,2-Metalate Rearrangements 306

9.5 Carbocupration 309

10 Mechanisms of Copper-mediated Addition and Substitution Reactions / Seiji Mori, Eiichi Nakamura 315

10.2 Conjugate Addition Reaction 318

10.2.1 Four-centered and Six-centered Mechanisms 318

10.2.2 Single-electron Transfer Theorem 319

10.2.3 Kinetic and Spectroscopic Analysis of Intermediates 320

10.2.4 Catalytic Conjugate Addition 322

10.2.5 Theoretically Based Conjugate Addition Reaction Pathway 322

10.3 Carbocupration Reactions of Acetylenes and Olefins 324

10.3.2 Theoretically Based Carbocupration Reaction Pathway 325

10.4 Substitution Reactions on Carbon Atoms 327

10.4.1 S[subscript N]2 Mechanism of Stoichiometric Substitution Reactions 327

10.4.2 S[subscript N]2' Allylation Reactions 329

10.4.3 Radical Substitution Reaction Mechanisms 330

10.4.4 Catalytic Substitution Reactions 330

10.4.5 Theoretically Based Alkylation Reaction Pathways 330

10.6.1 Counter-cation Lewis Acid Effects 332

10.6.2 Me[subscript 3]SiCl Acceleration 333

10.6.3 Dummy Ligands 335

10.6.4 The "Higher Order" Cuprate Controversy 337

10.7 Orbital Interactions in Copper-mediated Reactions 338

10.8 The Roles of Cluster Structure in Copper-mediated Reactions 339.

Notes:

Includes bibliographical references and indexes.

ISBN:

3527297731

OCLC:

47676544