Grignard Reagents New Developments

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ISBN: 9780471999089 | 0471999083
Cover: Hardcover
Copyright: 1/26/1999

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The Grignard reagent is one of the most useful and versatile reagents known to the organic chemist and 100 years after its discovery, this book presents authoritative perspectives on the significant developments taking place using Grignard Reagents and related organomagnesium compounds.This volume focuses on a dozen areas of organomagnesium chemistry, including:* New reactions of Grignard Reagents* Stereoselective Reactions of Organomagnesium Compounds* Mechanistic Features of Organomagnesium Compounds* Industrial Applications and Strategy* Unusual Organomagnesium Compounds* Structures of Organomagnesium Solids and SolutionsThe book will prove of great interest to academic and industrial chemists active in organometallic chemistry of main group metals, organic syntheses, reaction mechanisms and structural organic chemistry.

List of Contributors

xiii

Preface

Mechanistic Features of the Reactions of Organomagnesium Compounds

(26)

Torkil Holm

Ingolf Crossland

Introduction

(2)

Properties of Grignard Reagents

(4)

Thermochemistry

(1)

Heat of Formation of Grignard Reagents

(1)

C---Mg Bond Dissociation Energies

(1)

Oxidation Potentials of Grignard Reagents

(1)

Association Equilibria in Grignard Reagents

(1)

The Schlenk Equilibrium

(1)

Self Association in Grignard Reagents

(1)

Association between RMgX and Carbonyl Compounds

(1)

Reactions of Benzophenone(s) with Grignard Reagents

(10)

Prediction of a Radical Mechanism and Early Evidence

(1)

Reactivity Series and Linear Free Energy Correlations

(3)

Radical Probes

(2)

A Thermochemical Approach

(1)

Kinetic Isotope Effects

(1)

Isotopic Carbon and Hydrogen in Benzophenone

(1)

Deuterium Substitution in the Grignard Reagent

(1)

CIDNP Observations

(1)

A New School in the Study of the Reaction of Benzophenone with Grignard Reagents

(1)

Polar Concerted Reaction Mechanisms

(2)

Addition to Aliphatic Ketones

(1)

Addition to Acid Derivatives

(1)

Concerted Transfer of β-Hydrogen. Reduction

(1)

Reactions with α, β-Unsaturated Carbonyl Compounds

(1)

ET Substrates other than Benzophenone

(4)

Metal Catalysis

(1)

The Kharasch Reaction

(1)

Reductive Dimerization of Carbonyl Compounds

(1)

Reaction with Oxygen and with Peroxides

(1)

Reactions with Azobenzene

(1)

Reactions with Cinnamic Esters

(1)

Solvent Effects

(1)

Conclusion

(3)

Nucleophilic Displacements at Carbon by Grignard Reagents

(38)

E. Alexander Hill

Introduction

(2)

Survey of Coupling Reactions of Grignard Reagents with Organic Halides

(1)

Reactions with `Simple' Alkyl Halides

(1)

Reactions with `Reactive' Halides

(1)

Summary of Cross-coupling Mechanisms

(9)

SN2 Displacement Mechanism

(2)

SN1 Mechanism

(1)

Single Electron Transfer (SET) Mechanism

(5)

Mechanism of Grignard Cross-coupling Reactions

(7)

Saturated Alkyl Halides

(1)

Benzylic and Allylic Grignard Reagents

(3)

Benzylic and Allylic Grignard Reagents

(1)

Benzylic and Allylic Halides

(2)

α-Haloethers and-Thioethers

(1)

Other Classes of Substrates

(11)

Arylmethyl Compounds

(2)

Polyhalogen Compounds

(1)

α-Haloketones

(1)

Other Leaving Groups

(1)

Reaction with Carbocations---No Leaving Group

(1)

Oxy-Anions

(5)

Miscellaneous Leaving Groups

(1)

Some Related Topics

(2)

Summary and Conclusions

(6)

Hydromagnesiation of Alkenes and Alkynes

(42)

Fumie Sato

Hirokazu Urabe

Introduction

(2)

Hydromagnesiation of Alkenes

(12)

Hydromagnesiation of Conjugated Dienes

(3)

Hydromagnesiation of Alkynes

(11)

Application of Hydromagnesiation in Selective Synthesis of Natural Products

(4)

On the Mechanism of Cp2 TiCl2-catalyzed Hydromagnesiation of alkynes with Grignard Reagents

(5)

Concluding Remarks

102

(5)

Stereoselective Addition of Grignard Reagents to Alkenes

107

(32)

Amir H. Hoveyda

Nicola M. Heron

Jeffrey A. Adams

Introduction

107

(1)

Heteroatom-directed Addition of Grignard Reagents to Alkenes

108

(1)

Zr-Catalyzed Diastereoselective Carbomagnesation of Allylic and Homoallylic Alcohols and Ethers

109

(5)

Zr-Catalyzed Diastereoselective Ethylmagnesation of Allylic Alcohols and Ethers

109

(3)

Zr-Catalyzed Diastereoselective Ethylmagnesation of Homoallylic Alcohols and Ethers

112

(2)

Zirconocene-catalyzed Enantioselective Alkylation Reactions

114

(12)

Catalytic Enantioselective Alkylation of Alkenes with Alkylmagnesium Halides

114

(5)

Zr-Catalyzed Kinetic Resolution of Unsaturated Heterocycles

119

(4)

Zr-Catalyzed Kinetic Resolution of Cyclic Allylic Ethers

123

(2)

Related Catalytic Enantioselective Alkylation of Alkenes with Alkylaluminums

125

(1)

Ni-Catalyzed Stereoselective Alkylation of Alkenes with Grignard Reagents

126

(9)

Diastereoselective Ni-Catalyzed Addition of Grignard Reagents to Allylic Ethers

128

(1)

Directed Ni-catalyzed Addition of Grignard Reagents to Allylic Ethers

128

(3)

Ni-catalyzed Addition of Grignard Reagents to Bicyclic Allylic Ethers

131

(1)

Asymmetric Ni-Catalyzed Addition of Grignard Reagents to Allylic Ethers

132

(2)

Asymmetric Ni-Catalyzed Addition of Grignard Reagents to Allylic Acetals

134

(1)

Summary and Outlook

135

(4)

Stereoselective Additions of Chiral Grignard Reagents to Aldehydes: Stereochemical and Mechanistic Principles, with Examples Using α-Amino Grignard Reagents

139

(26)

Robert E. Gawley

Introduction to Stereoselectivity in Grignard Additions

139

(2)

Transition States and Mechanistic Rationales

141

(2)

Topicity and Terminology

143

(2)

Additions of Configurationally Stable Grignards to Aldehydes

145

(1)

Configurational Lability of Benzylic Grignards

146

(2)

Additions of Benzylic Grignards to Aldehydes

148

(5)

Applications to Alkaloid Synthesis

153

(9)

Summary

162

(3)

Grignard Reagents---Industrial Applications and Strategy

165

(20)

Frank R. Busch

David M. De Antonis

Introduction

165

(1)

Safety and Engineering Considerations Specific to Industrial Applications

166

(5)

Typical Equipment Configuration

166

(1)

Choice of Solvent

167

(1)

Process Hazards Analysis

167

(1)

Vent Sizing/DIERS Calculations

168

(1)

Grignard Reagent Formation---Process Controls and Interlocks

168

(1)

Control of Exotherm

168

(2)

Safety Interlocks

170

(1)

Reactivity of Grignard Reagents---Water, Heating/Cooling Fluids

171

(1)

Safe Handling of Magnesium

171

(1)

Reaction Initiation

171

(4)

Equipment Drying

172

(1)

Different Forms of Magnesium: Advantages and Disadvantages

172

(1)

Initiators---Advantages and Disadvantages

173

(1)

Vitride®

173

(1)

Small Portion of Grignard Reagent

174

(1)

Chemical Initiators

174

(1)

Detecting Initiation of Reaction

175

(1)

Examples of Industrial Grignard Chemistry

175

(6)

Tamoxifen

175

(1)

Droloxifene

175

(1)

Veltol® and Veltol Plus®

176

(1)

Use of a Grignard Reagent as a Base (Formation of Magnesium Enolates)

176

(2)

Naproxen

178

(2)

Propoxyphene

180

(1)

Additional Examples

181

(1)

Waste Disposal

181

(1)

Summary

181

(4)

Mechanisms of Grignard Reagent Formation

185

(92)

John F. Garst

Ferenc Ungvary

Introduction

185

(6)

Grignard Reaction

185

(1)

Basic Facts

185

(1)

Overview

186

(3)

D and A Models

189

(1)

Occam's Razor

190

(1)

Organic Part of the Mechanism

191

(62)

Experimental Techniques

191

(2)

Rate Law

193

(1)

Radical Intermediates---Pathway R

193

(2)

Models, Rates, and Rate Constants

195

(3)

Kinetics of ZB and AB

198

(4)

Infinite-Dilution D Model

202

(1)

General D Model

203

(3)

Typical Alkyl Halides

206

(7)

Cyclopropyl Halides

213

(9)

Vinyl Halides

222

(1)

Aryl Halides

222

(3)

Benzylic and Allylic Halides

225

(1)

Area of the Magnesium Surface

226

(1)

Concentration of Halide

226

(1)

Halogen

227

(2)

Solvent

229

(1)

Adamantlyl Bromide

229

(1)

Slurries of Small Magnesium Clusters

230

(5)

Chain Mechanisms

235

(1)

Carbanion Intermediates

235

(3)

Anion-Radical Intermediates in Reductions of Organic Halides

238

(9)

Retention of Configuration, Adsorption of R., and the D Model

247

(1)

Arguments Against the D Model

248

(5)

Arguments Against the A Model

253

(1)

Inorganic Part of the Mechanism

253

(13)

Optical and Scanning-Electron Microscopy

253

(1)

Atomic-Force Microscopy (AFM)

254

(1)

Surface Spectroscopy

255

(1)

Initiation

255

(2)

Activation

257

(2)

Entrainment

259

(1)

Metallic Corrosion

259

(1)

Mg(I) Intermediates

260

(2)

Mgz-Solution Interface

262

(1)

Two Liquid Phases

263

(1)

Freckled Magnesium

264

(2)

Conclusions

266

(11)

Appendix

267

(10)

Applications of Magnesium Anthracene in Forming Grignard Reagents

277

(22)

Colin L. Raston

Introduction

277

(1)

Formation and Properties of Magnesium Anthracene

278

(3)

Reactions: General Considerations

281

(3)

Formation of Grignard Reagents

284

(6)

Mono-Grignard Reagents---Special Features

286

(2)

Di-and Tri-Grignard Reagents

288

(1)

Mechanism

289

(1)

Reactions of Other Organic Halides

290

(3)

Supported Magnesium Anthracene Complexes

293

(3)

Synthesis

293

(2)

Grignard Reagents

295

(1)

Polymer and Silica Recycling

296

(1)

Future Prospects

296

(3)

Structures of Organomagnesium Compounds as Revealed by X-ray Diffraction Studies

299

(30)

F. Bickelhaupt

Introduction

299

(1)

Magnesium with Coordination Number 2

300

(1)

Magnesium with Coordination Number 3

301

(1)

Simple Organomagnesium with Coordination Number 4

302

(4)

Mononuclear Compounds

302

(2)

Dimeric Compounds

304

(1)

Polymeric Compounds

305

(1)

Simple Organomagnesium with Coordination Number 5 and 6

306

(2)

Organomagnesium Compounds with Coordination Number 5

307

(1)

Organomagnesium Compounds with Coordination Number 6

308

(1)

Difunctional Organomagnesium Compounds

308

(4)

Simple Difunctional Organomagnesium Compounds

308

(3)

Organomagnesium Compounds Derived from Dienes or Diynes

311

(1)

Anthracenemagnesium Derivatives

311

(1)

Organomagnesium Compounds with Polyhapto Carbon Ligands

312

(2)

Cyclopentadienyl Derivatives and Related Compounds

312

(2)

Carborane Derivatives

314

(1)

Organomagnesium Compounds with Intramolecular and/or Polycoordination

314

(6)

Intramolecular Coordination

314

(2)

Intramolecular Polycoordination

316

(1)

Intermolecular Polycoordination

317

(3)

Hetermometallic Organomagnesium Complexes

320

(4)

Heterometallic Organomagnesium Complexes with Alkali Metals

320

(1)

Heterometallic Organomagnesium Complexes with Aluminum

321

(1)

Heterometallic Organomagnesium Complexes with Transition Metals

322

(2)

Conclusions

324

(5)

X-ray Absorption Spectroscopy and Large Angle X-ray Scattering of Grignard Compounds

329

(38)

T.S. Ertel

H. Bertagnolli

Introduction

329

(1)

EXAFS

330

(5)

Theoretical Background

330

(2)

Measurement Fundamentals and Techniques

332

(2)

Data Analysis

334

(1)

LAXS

335

(4)

Theoretical Background

335

(3)

Measurement Fundamentals and Techniques

338

(1)

Data Analysis

338

(1)

Comparison of EXAFS and LAXS Techniques

339

(1)

Physical Chemistry of Grignard Compounds

340

(7)

Introduction

340

(1)

Crystallography

341

(2)

Molecular Weight Studies

343

(1)

Tracer Studies

344

(1)

Conductivity Measurements

344

(1)

Infrared Spectroscopy

344

(1)

NMR Spectroscopy

345

(1)

Theoretical Studies

345

(2)

EXAFS and LAXS of Grignard Compounds

347

(16)

Introduction

347

(1)

EXAFS Studies

348

(11)

LAXS Studies

359

(4)

Concluding Remark: Current Structural Picture

363

(4)

Di-and Polyfunctional Organomagnesium Compounds

367

(28)

F. Bickelhaupt

Introduction

367

(2)

Di-organomagnesium Reagents

369

(3)

Synthesis and Structure

369

(1)

Applications

370

(2)

Di-organomagnesium Reagents

372

(3)

Synthesis and Structure

372

(2)

Applications

374

(1)

Di-organomagnesium Reagents

375

(5)

Synthesis and Structure

375

(2)

Applications

377

(3)

and Larger α, ω-Di-organomagnesium Reagents

380

(5)

Synthesis and Structure

380

(2)

Applications

382

(3)

Tri-and Polyorganomagnesium Reagents

385

(4)

Conclusion

389

(6)

Unusual Organomagnesium Compounds

395

(16)

V. V. Smirnov

L.A. Tjurina

I.P. Beletskaya

Introduction

395

(1)

Cluster Grignard Reagents

395

(6)

Metal Vapour Cryosynthesis

395

(1)

The Role of Clusters in the Low-Temperature Cryosynthesis of Organomagnesium Compounds

396

(1)

Cluster Grignard Reagents---Characterization

397

(2)

Cluster Grignard Reagents---Reactions with Organic Halides

399

(2)

Cluster Magnesium Hydrides

401

(9)

Theory

401

(2)

Magnesium-Hydrocarbon Cryosyntheses

403

(1)

Alkylbenzenes

403

(1)

Cyclopentadiene

404

(1)

Phenylacetylene

405

(1)

1-Alkenes

406

(1)

Anthracene

407

(2)

Catalytic Properties of Magnesium-Hydrocarbon Adducts

409

(1)

Conclusion

410

(1)

Index

411

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Grignard Reagents New Developments

Summary

Author Biography

Table of Contents

Supplemental Materials

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Grignard Reagents New Developments

Summary

Author Biography

Table of Contents

Supplemental Materials

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