Cycloaddition reactions in organic synthesis / edited by Shū Kobayashi and Karl Anker Jørgensen.

Format:

Book

Contributor:

Jørgensen, Karl Anker.

Kobayashi, S. (Shu), 1959-

Rosengarten Family Fund.

Language:

English

Subjects (All):

Ring formation (Chemistry).

Organic compounds--Synthesis.

Organic compounds.

Physical Description:

xii, 332 pages : illustrations ; 25 cm

Place of Publication:

Weinheim : Wiley-VCH, [2002]

Summary:

Cycloaddition reactions are among the most important tools for synthesis in organic chemistry, since these reactions are vital to the modern synthesis of natural products and biologically active substances. Metal catalysis plays an increasingly important role in these reactions, often allowing several stereocenters to be selectively created and integrated in the target molecules. Kobayashi and Jorgensen's handbook provides numerous examples of metal-catalyzed reactions, including [2+1], [3+2] and [4+2] cycloadditions. Important reactions such as carbo- and hetero-Diels-Alder, carbocyclic, cyclopropanation and 1,3-dipolar cycloaddition reactions are discussed. A large number of experimental procedures gives a concrete idea of the use of metal-catalyzed cycloaddition reactions in modern synthesis. The book is aimed at chemists in industry or academia, who want to effectively use cycloadditions in their work.

Contents:

1 Catalytic Asymmetric Diels-Alder Reactions / Yujiro Hayashi 5

1.2 The Chiral Lewis Acid-catalyzed Diels-Alder Reaction 6

1.2.1 The Asymmetric Diels-Alder Reaction of [alpha, beta]-Unsaturated Aldehydes as Dienophiles 6

1.2.1.1 Aluminum 6

1.2.1.2 Boron 6

1.2.1.3 Titanium 18

1.2.1.4 Iron 20

1.2.1.5 Ruthenium 21

1.2.1.6 Chromium 21

1.2.1.7 Copper 21

1.2.2 The Asymmetric Diels-Alder Reaction of [alpha, beta]-Unsaturated Esters as Dienophiles 23

1.2.3 The Asymmetric Diels-Alder Reaction of 3-Alkenoyl-1,3-oxazolidin-2-ones as Dienophiles 24

1.2.3.1 Aluminum 26

1.2.3.2 Magnesium 26

1.2.3.3 Copper 27

1.2.3.4 Iron 34

1.2.3.5 Nickel 34

1.2.3.6 Titanium 36

1.2.3.7 Zirconium 40

1.2.3.8 Lanthanides 40

1.2.4 The Asymmetric Diels-Alder Reaction of Other Dienophiles 43

1.3 The Asymmetric Catalytic Diels-Alder Reaction Catalyzed by Base 46

2 Recent Advances in Palladium-catalyzed Cycloadditions Involving Trimethylenemethane and its Analogs / Dominic M. T. Chan 57

2.2 Mechanism for [3+2] Carbocyclic Cycloaddition 58

2.3 Dynamic Behavior of TMM-Pd Complexes 59

2.4 Application in Organic Synthesis 60

2.4.2 [3+2] Cycloaddition: The Parent TMM

2.4.2.1 Recent Applications in Natural and Unnatural Product Synthesis 61

2.4.2.2 Novel Substrates for TMM Cycloaddition 61

2.4.3 [3+2] Cycloaddition: Substituted TMM 63

2.4.3.1 Cyclopropyl-substituted TMM 63

2.4.3.2 Phenylthio-TMM 64

2.4.4 [3+2] Cycloaddition: Intramolecular Versions 64

2.4.4.1 Introduction and Substrate Synthesis 64

2.4.4.2 Synthesis of Bicyclo[3.3.0]octyl Systems 65

2.4.4.3 Synthesis of Bicyclo[4.3.0]nonyl Systems 66

2.4.4.4 Synthesis of Bicyclo[5.3.0]decyl Systems 67

2.4.5 Carboxylative Cycloadditions 67

2.4.6 Carbonyl Cycloadditions 71

2.4.6.1 Addition to Aldehydes 71

2.4.6.2 Addition to Ketones 72

2.4.7 Imine Cycloadditions 73

2.4.8 [4+3] Cycloadditions 76

2.4.9 [6+3] Cycloadditions 80

2.4.10 [3+3] Cycloaddition 82

3 Enantioselective [2+1] Cycloaddition: Cyclopropanation with Zinc Carbenoids / Scott E. Denmark, Gregory Beutner 85

3.2 The Simmons-Smith Cyclopropanation

Historical Background 87

3.3 Structure and Dynamic Behavior of Zinc Carbenoids 90

3.3.1 Formation and Analysis of Zinc Carbenoids 90

3.3.2 Studies on the Schlenk Equilibrium for Zinc Carbenoids 93

3.4 Stereoselective Simmons-Smith Cyclopropanations 100

3.4.1 Substrate-directed Reactions 100

3.4.2 Auxiliary-directed Reactions 108

3.4.2.1 Chiral Ketals 108

3.4.2.2 Chiral Vinyl Ethers 111

3.4.3 In-situ Chiral Modification 115

3.4.3.1 Chirally Modified Reagents 115

3.4.3.2 Chirally Modified Substrates 118

3.4.4 Asymmetric Catalysis 121

3.4.4.1 General Considerations 121

3.4.4.2 Initial Discoveries 122

3.4.4.3 Defining the Role of Reaction Protocol 127

3.5 Simmons-Smith Cyclopropanations

Theoretical Investigations 140

4 Catalytic Enantioselective Cycloaddition Reactions of Carbonyl Compounds / Karl Anker Jorgensen 151

4.2 Activation of Carbonyl Compounds by Chiral Lewis Acids 151

4.2.1 The Basic Mechanisms of Cycloaddition Reactions of Carbonyl Compounds with Conjugated Dienes 152

4.3 Cycloaddition Reactions of Carbonyl Compounds 156

4.3.1 Reactions of Unactivated Aldehydes 156

4.3.1.1 Chiral Aluminum and Boron Complexes 156

4.3.1.2 Chiral Transition- and Lanthanide-metal Complexes 160

4.3.2 Reactions of Activated Aldehydes 164

4.3.2.1 Chiral Aluminum and Boron Complexes 164

4.3.3 Reactions of Ketones 174

4.3.4 Inverse Electron-demand Reactions 178

5 Catalytic Enantioselective Aza Diels-Alder Reactions / Shu Kobayashi 187

5.2 Aza Diels-Alder Reactions of Azadienes 188

5.3 Aza Diels-Alder Reactions of Azadienophiles 191

5.4 A Switch of Enantiofacial Selectivity 195

5.5 Chiral Catalyst Optimization 198

5.6 Aza Diels-Alder Reactions of [alpha]-Imino Esters with Dienes 203

5.7 Aza Diels-Alder Reactions of 2-Azadienes 205

5.8 Perspective 207

6 Asymmetric Metal-catalyzed 1,3-Dipolar Cycloaddition Reactions / Kurt Vesterager Gothelf 211

6.2 Basic Aspects of Metal-catalyzed 1,3-Dipolar Cycloaddition Reactions 212

6.2.1 The 1,3-Dipoles 212

6.2.2 Frontier Molecular Orbital Interactions 213

6.2.3 The Selectivities of 1,3-Dipolar Cycloaddition Reactions 216

6.3 Boron Catalysts for Reactions of Nitrones 218

6.4 Aluminum Catalysts for Reactions of Nitrones 219

6.5 Magnesium Catalysts for Reactions of Nitrones 224

6.6 Titanium Catalysts for Reactions of Nitrones and Diazoalkanes 226

6.7 Nickel Catalysts for Reactions of Nitrones 232

6.8 Copper Catalysts for Reactions of Nitrones 233

6.9 Zinc Catalysts for Reactions of Nitrones and Nitrile Oxides 235

6.10 Palladium Catalysts for Reactions of Nitrones 237

6.11 Lanthanide Catalysts for Reactions of Nitrones 239

6.12 Cobalt, Manganese, and Silver Catalysts for Reactions of Azomethine Ylides 240

6.13 Rhodium Catalysts for Reactions of Carbonyl Ylides 242

7 Aqua Complex Lewis Acid Catalysts for Asymmetric 3+2 Cycloaddition Reactions / Shuji Kanemasa 249

7.2 DBFOX/Ph-Transition Metal Complexes and Diels-Alder Reactions 250

7.2.1 Preparation and Structure of the Catalysts 250

7.2.2 Diels-Alder Reactions 252

7.2.3 Structure of the Substrate Complexes 255

7.2.4 Tolerance of the Catalysts 259

7.2.5 Nonlinear Effect 260

7.3 Nitrone and Nitronate Cycloadditions 268

7.3.1 Nickel(II) Complex-catalyzed Reactions 268

7.3.2 Role of MS 4 A 270

7.3.3 Nitronate Cycloadditions 272

7.3.4 Reactions of Monodentate Dipolarophiles 274

7.3.5 Transition Structures 276

7.4 Diazo Cycloadditions 278

7.4.1 Screening of Lewis Acid Catalysts 279

7.4.2 Zinc Complex-catalyzed Asymmetric Reactions 281

7.4.3 Transition Structures 283

7.5 Conjugate Additions 285

7.5.1 Thiol Conjugate Additions 285

7.5.2 Hydroxylamine Conjugate Additions 288

7.5.3 Michael Additions of Carbon Nucleophiles 291

8 Theoretical Calculations of Metal-catalyzed Cycloaddition Reactions / Karl Anker Jorgensen 301

8.2 Carbo-Diels-Alder Reactions 302

8.2.1 Frontier-molecular-orbital Interactions for Carbo-Diels-Alder Reactions 302

8.2.2 Activation of the Dienophile by Lewis Acids, Interactions, Reaction Course, and Transition-state Structures 303

8.3 Hetero-Diels-Alder Reactions 314

8.3.1 Frontier-molecular-orbital Interactions for Hetero-Diels-Alder Reactions 314

8.3.2 Normal Electron-demand Hetero-Diels-Alder Reactions 315

8.3.3 Inverse Electron-demand Hetero-Diels-Alder Reactions 319

8.4 1,3-Dipolar Cycloaddition Reactions of Nitrones 321

8.4.1 Frontier-orbital Interactions for 1,3-Dipolar Cycloaddition Reactions of Nitrones 321

8.4.2 Normal Electron-demand Reactions 322

8.4.3 Inverse Electron-demand Reactions 323.

Notes:

Includes bibliographical references and index.

Local Notes:

Acquired for the Penn Libraries with assistance from the Rosengarten Family Fund.

ISBN:

3527301593

OCLC:

46909954