Chiral sulfur ligands : asymmetric catalysis / Hélène Pellissier.

Format:

Book

Author/Creator:

Pellissier, Hélène.

Contributor:

Alumni and Friends Memorial Book Fund.

Series:

RSC catalysis series

Language:

English

Subjects (All):

Asymmetric synthesis.

Chirality.

Ligands (Biochemistry).

Catalysis.

Sulfur.

Physical Description:

xiv, 387 pages : illustrations ; 24 cm.

Place of Publication:

Cambridge, UK : Royal Society of Chemistry, [2009]

Summary:

The preparation of chiral compounds is an important area of contemporary synthetic organic chemistry. Most natural products are chiral and their physiological or pharmacological properties depend upon their recognition by chiral receptors. The use of chiral drugs in the enantiopure form is now a standard requirement and the development of new synthetic methods to obtain enantiopure compounds has become a key objective for pharmaceutical companies.

The growing number of reports dealing with the use of chiral sulfur-containing ligands for asymmetric catalysis is representative of the success of such ligands to promote numerous catalytic transformations. Whereas the synthesis of chiral phosphorus ligands is often complex and difficult, the preparation of chiral sulfur compounds is much more convenient. Consequently, a wide diversity of chiral sulfur-containing ligands is readily available, either directly from the chiral pool or by facile modifications of other heteroatomic ligands. Many of the sulfur-containing ligands have only recently appeared in the literature, and it is clear that their application in asymmetric catalysis will increase in the near future due in part to their easy synthesis. Asymmetric heterogeneous catalysis seems to be a good way to develop the potential of these ligands in an economic and environmentally friendly manner.

The goal of this book is to provide researchers and professionals of academic and industrial laboratories with a broad overview of the works concerning the use of chiral sulfur-containing ligands in one of the most important focal areas in organic synthesis, asymmetric catalysis. The book is divided into ten chapters corresponding to the different types of reactions based on the use of complexes containing chiral sulfur ligands.

Contents:

Chapter 1 Allylic Substitution 7

1.1 Introduction 7

1.2 S/S Ligands 10

1.3 S/P Ligands 15

1.4 S/N Ligands 26

1.5 S/C and S/O Ligands 40

1.6 Sulfur-Containing P/N, P/O, N/N, N/O and P/P Ligands 41

1.7 Sulfur-Containing Ferrocenyl Ligands 53

1.8 Conclusions 64

References 65

Chapter 2 Conjugate Addition 74

2.1 Introduction 74

2.2 Copper Catalysts 75

2.3 Other Metal Catalysts 96

2.4 Conclusions 101

References 101

Chapter 3 Addition of Organometallic Reagents to Aldehydes 105

3.1 Introduction 105

3.2 Addition of Organozinc Reagents to Aldehydes 106

3.2.1 Addition of Dialkylzinc Reagents to Aldehydes 106

3.2.1.1 S/N Ligands 106

3.2.1.2 S/N/O Ligands 119

3.2.1.3 S/O Ligands 138

3.2.1.4 Sulfur-Containing Ferrocenyl Ligands 141

3.2.2 Addition of Aryl-, Alkenyl-and Alkynylzinc Reagents to Aldehydes 142

3.3 Addition of Organometallic Reagents other than Organozinc Reagents 147

3.4 Conclusions 150

References 150

Chapter 4 Addition of Organozinc Reagents to Ketones 156

References 181

Chapter 5 Diels-Aider Reaction 184

References 205

Chapter 6 Cyclopropanation 208

6.1 Introduction 208

6.2 Transition-Meial-Catalysed Decomposition of Diazoalkanes 209

6.2.1 Sulfide Ligands 210

6.2.2 Thiophene Ligands 210

6.2.3 Sulfoxide Ligands 214

6.2.4 Sulfonamide Ligands 214

6.3 Simmons-Smith Cyclopropanation 222

6.4 Conclusions 228

References 229

Chapter 7 Heck-Type Reactions 233

References 241

Chapter 8 Hydrogenation 243

8.1 Introduction 243

8.2 Hydrogenation of Olefins 243

8.3 Hydrogenation of Ketones 259

8.4 Conclusions 267

References 268

Chapter 9 Hydrogen Transfer 270

References 290

Chapter 10 Miscellaneous Reactions 293

10.1 Introduction 293

10.2 Hydroformyiation 293

10.3 1,3-Dipolar Cycloaddition 296

10.4 [2+2] Cycloaddition 304

10.5 Carbonyl Ene Reaction 306

10.6 Addition of Diethylzinc to Imines 307

10.7 Allylstannation of Ketones 310

10.8 Allylsilylation of Carbonyl Compounds 311

10.9 Aldol-Type Reaction 313

10.10 Mannich-Type Reaction 320

10.11 Claisen Rearrangement 321

10.12 Epoxidation 324

10.13 Silyfcyanation 327

10.14 Hydrosilylation 329

10.15 Borane Reduction 336

10.16 Pauson-Khand Reaction 344

10.17 Radical C-C Bond-Forming Reaction 348

10.18 Ring Opening of Mesoheterobicyclic Alkenes 348

10.19 Bisalkoxycarbonyiation of Olefins 350

10.20 C-H Insertion 351

10.21 Hydroamination and Amination 356

10.22 Reissert Reaction 359

10.23 Aziridination 360

10.24 Grignard Crosscoupling 362

10.25 Conclusions 367

General Conclusion 368

References 370.

Notes:

Includes bibliographical references and index.

Local Notes:

Acquired for the Penn Libraries with assistance from the Alumni and Friends Memorial Book Fund.

ISBN:

9781847559241

1847559247

OCLC:

428777597

Publisher Number:

99936117274