Chemical Synthesis Using Highly Reactive Metals

Reuben D. Rieke, PhD, is internationally recognized for his pioneering work in the development of highly reactive metals, the synthesis of highly regioregular 3-alkylpolythiophenes, and novel organometallic reagents. In 1991, Dr. Rieke founded Rieke Metals, Inc.  He has 38 years of academic experience teaching organic chemistry and has published over 225 papers and been awarded over 25 patents.

Preface xvii

1 Genesis of Highly Reactive Metals 1

2 General Methods of Preparation and Properties 5

2.1 General Methods for Preparation of Highly Reactive Metals 5

2.2 Physical Characteristics of Highly Reactive Metal Powders 8

2.3 Origin of the Metals’ High Reactivity 9

References 10

3 Zinc 13

3.1 General Methods for Preparation of Rieke Zinc 13

3.2 Direct Oxidative Addition of Reactive Zinc to Functionalized Alkyl, Aryl, and Vinyl Halides 16

3.3 Reactions of Organozinc Reagents with Acid Chlorides 20

3.4 Reactions of Organozinc Reagents with α,β�-Unsaturated Ketones 27

3.5 Reactions of Organozinc Reagents with Allylic and Alkynyl Halides 30

3.6 Negishi Cross�-Coupling of Vinyl and Aryl Organozinc Halides 34

3.7 Intramolecular Cyclizations and Conjugate Additions Mediated by Rieke Zinc 42

3.8 The Formation and Chemistry of Secondary and Tertiary Alkylzinc Halides 44

3.9 Electrophilic Amination of Organozinc Halides 50

3.10 Reformatsky and Reformatsky�-Like Reagents and Their Chemistry 52

3.11 Configurationally Stable Organozinc Reagents and Intramolecular Insertion Reactions 54

3.12 Preparation of Tertiary Amides via Aryl, Heteroaryl, and Benzyl Organozinc Reagents 55

3.13 Preparation of 5�-Substituted�-2�-Furaldehydes 61

3.14 Preparation and Chemistry of 4�-Coumarylzinc Bromide 73

3.15 Preparation and Cross�-Coupling of 2�-Pyridyl and 3�-Pyridylzinc Bromides 77

3.16 Preparation of Functionalized α�-Chloromethyl Ketones 106

3.17 Rieke Zinc as a Reducing Agent for Common Organic Functional Groups 108

3.18 Detailed Studies on the Mechanism of Organic Halide Oxidative Addition at a Zinc Metal Surface 111

3.19 Regiocontrolled Synthesis of Poly(3�-Alkylthiophenes) Mediated by Rieke Zinc: A New Class of Plastic Semiconductors 133

4 Magnesium 161

4.1 General Background and Mechanistic Details of Grignard Reaction 161

4.2 General Methods for Preparation of Rieke Magnesium 165

4.3 Grignard Reagent Formation and Range of Reactivity of Magnesium 167

4.4 1,3�-Diene�-Magnesium Complexes and Their Chemistry 172

4.5 Regioselectivity of Reaction of Complexes with Electrophiles 173

4.6 Carbocyclization of (1,4�-Diphenyl�-2�-butene�-1,4�-diyl) magnesium with Organic Dihalides 175

4.7 1,2�-Dimethylenecycloalkane�-Magnesium Reagents 175

4.8 Synthesis of Fused Carbocycles, β�-γ�-Unsaturated Ketones, and 3�-Cyclopentenols from Conjugated Diene�-Magnesium Reagents 178

4.9 Synthesis of Spiro�-γ�-Lactones and Spiro�-δ�-Lactones from 1,3�-Diene�-Magnesium Reagents 184

4.10 Synthesis of γ�-Lactams from Conjugated Diene�-Magnesium Reagents 190

4.11 Low�-Temperature Grignard Chemistry 192

4.12 Typical Procedures for Preparation of Active Magnesium and Typical Grignard Reactions as Well as 1,3�-Diene Chemistry 197

5 Copper 209

5.1 Background of Copper and Organocopper Chemistry 209

5.2 Development of Rieke Copper 210

5.3 Phosphine�-Based Copper 211

5.4 Lithium 2�-Thienylcyanocuprate�-Based Copper 220

5.5 Copper Cyanide�-Based Active Copper 224

5.6 Formal Copper Anion Preparation and Resulting Chemistry 228

5.7 Typical Experimental Details of Copper Chemistry 232

6 Indium 241

6.1 Background and Synthesis of Rieke Indium 241

6.2 Preparation of Organoindium Compounds 241

6.3 Preparation and Reactions of Indium Reformatsky Reagents 246

6.4 Experimental Details for Preparation and Reactions of Activated Indium 250

7 Nickel 255

7.1 Preparation of Rieke Nickel, Characterization of Active Nickel Powder, and Some Chemistry 255

7.2 Preparation of 3�-Aryl�-2�-hydroxy�-1�-propane by Nickel�-Mediated Addition of Benzylic Halides to 1,2�-Diketones 261

7.3 Preparation of 3�-Arylpropanenitriles by Nickel�-Mediated Reaction of Benzylic Halides with Haloacetonitriles 265

7.4 Reformatsky�-Type Additions of Haloacetonitriles to Aldehydes Mediated by Metallic Nickel 267

7.5 Preparation of Symmetrical 1,3�-Diarylpropan�-2�-ones from Benzylic Halides and Alkyl Oxalyl Chlorides 269

7.6 Nickel�-Mediated Coupling of Benzylic Halides and Acyl Halides to Yield Benzyl Ketones 273

7.7 Nickel�-Assisted Room Temperature Generation and Diels–Alder Chemistry of o�-Xylylene Intermediates 275

8 Manganese 305

8.1 Preparation of Rieke Manganese 305

8.2 Direct Formation of Aryl�-, Alkyl�-, and Vinylmanganese Halides Oxidative Addition of the Active Metal to the Corresponding Halide 306

8.3 Direct Formation of Organomanganese Tosylates and Mesylates and Some Cross�-Coupling Reactions 316

8.4 Benzylic Manganese Halides, Sulfonates, and Phosphates: Preparation, Coupling Reactions, and Applications in New Reactions 320

8.5 Preparation and Coupling Reactions of Thienylmanganese Halides 339

8.6 Synthesis of β�-Hydroxy Esters Using Active Manganese 343

8.7 Reductive Coupling of Carbonyl�-Containing Compounds and Imines Using Reactive Manganese 347

8.8 Preparation of Heteroarylmanganese Reagents and Their Cross�-Coupling Chemistry 355

9 Calcium 371

9.1 Preparation of Rieke Calcium 371

9.2 Oxidative Addition Reactions of Rieke Calcium with Organic Halides and Some Subsequent Reactions 372

9.3 Preparation and Reaction of Calcium Cuprate Reagents 373

9.4 Preparation and Reactions of Calcium Metallocycles 377

9.5 Synthesis of Polyphenylcarbynes Using Highly Reactive Calcium, Barium, and Strontium: A Precursor for

9.6 Chemical Modification of Halogenated Polystyrenes Using Rieke Calcium or Rieke Copper 386

10 Barium 391

10.1 Preparation of Rieke Barium 391

10.2 Oxidative Addition of Rieke Barium to Allylic Halides: Preparation of Stereochemically Homogeneous Allylic Barium Reagents 392

11 Iron 395

11.1 Preparation of Highly Reactive Iron and Some Oxidative Addition Chemistry 395

12 Palladium and Platinum 399

12.1 Preparation of Highly Reactive Palladium and Platinum and Some Oxidative Addition Chemistry 399

13 Highly Reactive Uranium and Thorium 407

13.1 Two Methods for Preparation of Highly Reactive Uranium and Thorium: Use of a Novel Reducing Agent Naphthalene Dianion 407

14 Aluminum 425

14.1 Preparation of Highly Reactive Aluminum and Reaction with Aryl Halides 425

15 Cobalt 429

15.1 Two Methods for Preparing Rieke Cobalt: Reaction with CO and Also Fischer–Tropsch Chemistry 429

16 Chromium 443

16.1 Preparation of Highly Reactive Chromium Metal and Its Reaction with CO to Yield Cr(CO)6 443

References 446

Index 447

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