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 xvii1 Genesis of Highly Reactive Metals 12 General Methods of Preparation and Properties 52.1 General Methods for Preparation of Highly Reactive Metals 52.2 Physical Characteristics of Highly Reactive Metal Powders 82.3 Origin of the Metals’ High Reactivity 9References 103 Zinc 133.1 General Methods for Preparation of Rieke Zinc 133.2 Direct Oxidative Addition of Reactive Zinc to Functionalized Alkyl, Aryl, and Vinyl Halides 163.3 Reactions of Organozinc Reagents with Acid Chlorides 203.4 Reactions of Organozinc Reagents with α,β-Unsaturated Ketones 273.5 Reactions of Organozinc Reagents with Allylic and Alkynyl Halides 303.6 Negishi Cross-Coupling of Vinyl and Aryl Organozinc Halides 343.7 Intramolecular Cyclizations and Conjugate Additions Mediated by Rieke Zinc 423.8 The Formation and Chemistry of Secondary and Tertiary Alkylzinc Halides 443.9 Electrophilic Amination of Organozinc Halides 503.10 Reformatsky and Reformatsky-Like Reagents and Their Chemistry 523.11 Configurationally Stable Organozinc Reagents and Intramolecular Insertion Reactions 543.12 Preparation of Tertiary Amides via Aryl, Heteroaryl, and Benzyl Organozinc Reagents 553.13 Preparation of 5-Substituted-2-Furaldehydes 613.14 Preparation and Chemistry of 4-Coumarylzinc Bromide 733.15 Preparation and Cross-Coupling of 2-Pyridyl and 3-Pyridylzinc Bromides 773.16 Preparation of Functionalized α-Chloromethyl Ketones 1063.17 Rieke Zinc as a Reducing Agent for Common Organic Functional Groups 1083.18 Detailed Studies on the Mechanism of Organic Halide Oxidative Addition at a Zinc Metal Surface 1113.19 Regiocontrolled Synthesis of Poly(3-Alkylthiophenes) Mediated by Rieke Zinc: A New Class of Plastic Semiconductors 1334 Magnesium 1614.1 General Background and Mechanistic Details of Grignard Reaction 1614.2 General Methods for Preparation of Rieke Magnesium 1654.3 Grignard Reagent Formation and Range of Reactivity of Magnesium 1674.4 1,3-Diene-Magnesium Complexes and Their Chemistry 1724.5 Regioselectivity of Reaction of Complexes with Electrophiles 1734.6 Carbocyclization of (1,4-Diphenyl-2-butene-1,4-diyl) magnesium with Organic Dihalides 1754.7 1,2-Dimethylenecycloalkane-Magnesium Reagents 1754.8 Synthesis of Fused Carbocycles, β-γ-Unsaturated Ketones, and 3-Cyclopentenols from Conjugated Diene-Magnesium Reagents 1784.9 Synthesis of Spiro-γ-Lactones and Spiro-δ-Lactones from 1,3-Diene-Magnesium Reagents 1844.10 Synthesis of γ-Lactams from Conjugated Diene-Magnesium Reagents 1904.11 Low-Temperature Grignard Chemistry 1924.12 Typical Procedures for Preparation of Active Magnesium and Typical Grignard Reactions as Well as 1,3-Diene Chemistry 1975 Copper 2095.1 Background of Copper and Organocopper Chemistry 2095.2 Development of Rieke Copper 2105.3 Phosphine-Based Copper 2115.4 Lithium 2-Thienylcyanocuprate-Based Copper 2205.5 Copper Cyanide-Based Active Copper 2245.6 Formal Copper Anion Preparation and Resulting Chemistry 2285.7 Typical Experimental Details of Copper Chemistry 2326 Indium 2416.1 Background and Synthesis of Rieke Indium 2416.2 Preparation of Organoindium Compounds 2416.3 Preparation and Reactions of Indium Reformatsky Reagents 2466.4 Experimental Details for Preparation and Reactions of Activated Indium 2507 Nickel 2557.1 Preparation of Rieke Nickel, Characterization of Active Nickel Powder, and Some Chemistry 2557.2 Preparation of 3-Aryl-2-hydroxy-1-propane by Nickel-Mediated Addition of Benzylic Halides to 1,2-Diketones 2617.3 Preparation of 3-Arylpropanenitriles by Nickel-Mediated Reaction of Benzylic Halides with Haloacetonitriles 2657.4 Reformatsky-Type Additions of Haloacetonitriles to Aldehydes Mediated by Metallic Nickel 2677.5 Preparation of Symmetrical 1,3-Diarylpropan-2-ones from Benzylic Halides and Alkyl Oxalyl Chlorides 2697.6 Nickel-Mediated Coupling of Benzylic Halides and Acyl Halides to Yield Benzyl Ketones 2737.7 Nickel-Assisted Room Temperature Generation and Diels–Alder Chemistry of o-Xylylene Intermediates 2758 Manganese 3058.1 Preparation of Rieke Manganese 3058.2 Direct Formation of Aryl-, Alkyl-, and Vinylmanganese Halides Oxidative Addition of the Active Metal to the Corresponding Halide 3068.3 Direct Formation of Organomanganese Tosylates and Mesylates and Some Cross-Coupling Reactions 3168.4 Benzylic Manganese Halides, Sulfonates, and Phosphates: Preparation, Coupling Reactions, and Applications in New Reactions 3208.5 Preparation and Coupling Reactions of Thienylmanganese Halides 3398.6 Synthesis of β-Hydroxy Esters Using Active Manganese 3438.7 Reductive Coupling of Carbonyl-Containing Compounds and Imines Using Reactive Manganese 3478.8 Preparation of Heteroarylmanganese Reagents and Their Cross-Coupling Chemistry 3559 Calcium 3719.1 Preparation of Rieke Calcium 3719.2 Oxidative Addition Reactions of Rieke Calcium with Organic Halides and Some Subsequent Reactions 3729.3 Preparation and Reaction of Calcium Cuprate Reagents 3739.4 Preparation and Reactions of Calcium Metallocycles 3779.5 Synthesis of Polyphenylcarbynes Using Highly Reactive Calcium, Barium, and Strontium: A Precursor for9.6 Chemical Modification of Halogenated Polystyrenes Using Rieke Calcium or Rieke Copper 38610 Barium 39110.1 Preparation of Rieke Barium 39110.2 Oxidative Addition of Rieke Barium to Allylic Halides: Preparation of Stereochemically Homogeneous Allylic Barium Reagents 39211 Iron 39511.1 Preparation of Highly Reactive Iron and Some Oxidative Addition Chemistry 39512 Palladium and Platinum 39912.1 Preparation of Highly Reactive Palladium and Platinum and Some Oxidative Addition Chemistry 39913 Highly Reactive Uranium and Thorium 40713.1 Two Methods for Preparation of Highly Reactive Uranium and Thorium: Use of a Novel Reducing Agent Naphthalene Dianion 40714 Aluminum 42514.1 Preparation of Highly Reactive Aluminum and Reaction with Aryl Halides 42515 Cobalt 42915.1 Two Methods for Preparing Rieke Cobalt: Reaction with CO and Also Fischer–Tropsch Chemistry 42916 Chromium 44316.1 Preparation of Highly Reactive Chromium Metal and Its Reaction with CO to Yield Cr(CO)6 443References 446Index 447

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 xvii1 Genesis of Highly Reactive Metals 12 General Methods of Preparation and Properties 52.1 General Methods for Preparation of Highly Reactive Metals 52.2 Physical Characteristics of Highly Reactive Metal Powders 82.3 Origin of the Metals’ High Reactivity 9References 103 Zinc 133.1 General Methods for Preparation of Rieke Zinc 133.2 Direct Oxidative Addition of Reactive Zinc to Functionalized Alkyl, Aryl, and Vinyl Halides 163.3 Reactions of Organozinc Reagents with Acid Chlorides 203.4 Reactions of Organozinc Reagents with α,β-Unsaturated Ketones 273.5 Reactions of Organozinc Reagents with Allylic and Alkynyl Halides 303.6 Negishi Cross-Coupling of Vinyl and Aryl Organozinc Halides 343.7 Intramolecular Cyclizations and Conjugate Additions Mediated by Rieke Zinc 423.8 The Formation and Chemistry of Secondary and Tertiary Alkylzinc Halides 443.9 Electrophilic Amination of Organozinc Halides 503.10 Reformatsky and Reformatsky-Like Reagents and Their Chemistry 523.11 Configurationally Stable Organozinc Reagents and Intramolecular Insertion Reactions 543.12 Preparation of Tertiary Amides via Aryl, Heteroaryl, and Benzyl Organozinc Reagents 553.13 Preparation of 5-Substituted-2-Furaldehydes 613.14 Preparation and Chemistry of 4-Coumarylzinc Bromide 733.15 Preparation and Cross-Coupling of 2-Pyridyl and 3-Pyridylzinc Bromides 773.16 Preparation of Functionalized α-Chloromethyl Ketones 1063.17 Rieke Zinc as a Reducing Agent for Common Organic Functional Groups 1083.18 Detailed Studies on the Mechanism of Organic Halide Oxidative Addition at a Zinc Metal Surface 1113.19 Regiocontrolled Synthesis of Poly(3-Alkylthiophenes) Mediated by Rieke Zinc: A New Class of Plastic Semiconductors 1334 Magnesium 1614.1 General Background and Mechanistic Details of Grignard Reaction 1614.2 General Methods for Preparation of Rieke Magnesium 1654.3 Grignard Reagent Formation and Range of Reactivity of Magnesium 1674.4 1,3-Diene-Magnesium Complexes and Their Chemistry 1724.5 Regioselectivity of Reaction of Complexes with Electrophiles 1734.6 Carbocyclization of (1,4-Diphenyl-2-butene-1,4-diyl) magnesium with Organic Dihalides 1754.7 1,2-Dimethylenecycloalkane-Magnesium Reagents 1754.8 Synthesis of Fused Carbocycles, β-γ-Unsaturated Ketones, and 3-Cyclopentenols from Conjugated Diene-Magnesium Reagents 1784.9 Synthesis of Spiro-γ-Lactones and Spiro-δ-Lactones from 1,3-Diene-Magnesium Reagents 1844.10 Synthesis of γ-Lactams from Conjugated Diene-Magnesium Reagents 1904.11 Low-Temperature Grignard Chemistry 1924.12 Typical Procedures for Preparation of Active Magnesium and Typical Grignard Reactions as Well as 1,3-Diene Chemistry 1975 Copper 2095.1 Background of Copper and Organocopper Chemistry 2095.2 Development of Rieke Copper 2105.3 Phosphine-Based Copper 2115.4 Lithium 2-Thienylcyanocuprate-Based Copper 2205.5 Copper Cyanide-Based Active Copper 2245.6 Formal Copper Anion Preparation and Resulting Chemistry 2285.7 Typical Experimental Details of Copper Chemistry 2326 Indium 2416.1 Background and Synthesis of Rieke Indium 2416.2 Preparation of Organoindium Compounds 2416.3 Preparation and Reactions of Indium Reformatsky Reagents 2466.4 Experimental Details for Preparation and Reactions of Activated Indium 2507 Nickel 2557.1 Preparation of Rieke Nickel, Characterization of Active Nickel Powder, and Some Chemistry 2557.2 Preparation of 3-Aryl-2-hydroxy-1-propane by Nickel-Mediated Addition of Benzylic Halides to 1,2-Diketones 2617.3 Preparation of 3-Arylpropanenitriles by Nickel-Mediated Reaction of Benzylic Halides with Haloacetonitriles 2657.4 Reformatsky-Type Additions of Haloacetonitriles to Aldehydes Mediated by Metallic Nickel 2677.5 Preparation of Symmetrical 1,3-Diarylpropan-2-ones from Benzylic Halides and Alkyl Oxalyl Chlorides 2697.6 Nickel-Mediated Coupling of Benzylic Halides and Acyl Halides to Yield Benzyl Ketones 2737.7 Nickel-Assisted Room Temperature Generation and Diels–Alder Chemistry of o-Xylylene Intermediates 2758 Manganese 3058.1 Preparation of Rieke Manganese 3058.2 Direct Formation of Aryl-, Alkyl-, and Vinylmanganese Halides Oxidative Addition of the Active Metal to the Corresponding Halide 3068.3 Direct Formation of Organomanganese Tosylates and Mesylates and Some Cross-Coupling Reactions 3168.4 Benzylic Manganese Halides, Sulfonates, and Phosphates: Preparation, Coupling Reactions, and Applications in New Reactions 3208.5 Preparation and Coupling Reactions of Thienylmanganese Halides 3398.6 Synthesis of β-Hydroxy Esters Using Active Manganese 3438.7 Reductive Coupling of Carbonyl-Containing Compounds and Imines Using Reactive Manganese 3478.8 Preparation of Heteroarylmanganese Reagents and Their Cross-Coupling Chemistry 3559 Calcium 3719.1 Preparation of Rieke Calcium 3719.2 Oxidative Addition Reactions of Rieke Calcium with Organic Halides and Some Subsequent Reactions 3729.3 Preparation and Reaction of Calcium Cuprate Reagents 3739.4 Preparation and Reactions of Calcium Metallocycles 3779.5 Synthesis of Polyphenylcarbynes Using Highly Reactive Calcium, Barium, and Strontium: A Precursor for9.6 Chemical Modification of Halogenated Polystyrenes Using Rieke Calcium or Rieke Copper 38610 Barium 39110.1 Preparation of Rieke Barium 39110.2 Oxidative Addition of Rieke Barium to Allylic Halides: Preparation of Stereochemically Homogeneous Allylic Barium Reagents 39211 Iron 39511.1 Preparation of Highly Reactive Iron and Some Oxidative Addition Chemistry 39512 Palladium and Platinum 39912.1 Preparation of Highly Reactive Palladium and Platinum and Some Oxidative Addition Chemistry 39913 Highly Reactive Uranium and Thorium 40713.1 Two Methods for Preparation of Highly Reactive Uranium and Thorium: Use of a Novel Reducing Agent Naphthalene Dianion 40714 Aluminum 42514.1 Preparation of Highly Reactive Aluminum and Reaction with Aryl Halides 42515 Cobalt 42915.1 Two Methods for Preparing Rieke Cobalt: Reaction with CO and Also Fischer–Tropsch Chemistry 42916 Chromium 44316.1 Preparation of Highly Reactive Chromium Metal and Its Reaction with CO to Yield Cr(CO)6 443References 446Index 447

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 xvii1 Genesis of Highly Reactive Metals 12 General Methods of Preparation and Properties 52.1 General Methods for Preparation of Highly Reactive Metals 52.2 Physical Characteristics of Highly Reactive Metal Powders 82.3 Origin of the Metals’ High Reactivity 9References 103 Zinc 133.1 General Methods for Preparation of Rieke Zinc 133.2 Direct Oxidative Addition of Reactive Zinc to Functionalized Alkyl, Aryl, and Vinyl Halides 163.3 Reactions of Organozinc Reagents with Acid Chlorides 203.4 Reactions of Organozinc Reagents with α,β-Unsaturated Ketones 273.5 Reactions of Organozinc Reagents with Allylic and Alkynyl Halides 303.6 Negishi Cross-Coupling of Vinyl and Aryl Organozinc Halides 343.7 Intramolecular Cyclizations and Conjugate Additions Mediated by Rieke Zinc 423.8 The Formation and Chemistry of Secondary and Tertiary Alkylzinc Halides 443.9 Electrophilic Amination of Organozinc Halides 503.10 Reformatsky and Reformatsky-Like Reagents and Their Chemistry 523.11 Configurationally Stable Organozinc Reagents and Intramolecular Insertion Reactions 543.12 Preparation of Tertiary Amides via Aryl, Heteroaryl, and Benzyl Organozinc Reagents 553.13 Preparation of 5-Substituted-2-Furaldehydes 613.14 Preparation and Chemistry of 4-Coumarylzinc Bromide 733.15 Preparation and Cross-Coupling of 2-Pyridyl and 3-Pyridylzinc Bromides 773.16 Preparation of Functionalized α-Chloromethyl Ketones 1063.17 Rieke Zinc as a Reducing Agent for Common Organic Functional Groups 1083.18 Detailed Studies on the Mechanism of Organic Halide Oxidative Addition at a Zinc Metal Surface 1113.19 Regiocontrolled Synthesis of Poly(3-Alkylthiophenes) Mediated by Rieke Zinc: A New Class of Plastic Semiconductors 1334 Magnesium 1614.1 General Background and Mechanistic Details of Grignard Reaction 1614.2 General Methods for Preparation of Rieke Magnesium 1654.3 Grignard Reagent Formation and Range of Reactivity of Magnesium 1674.4 1,3-Diene-Magnesium Complexes and Their Chemistry 1724.5 Regioselectivity of Reaction of Complexes with Electrophiles 1734.6 Carbocyclization of (1,4-Diphenyl-2-butene-1,4-diyl) magnesium with Organic Dihalides 1754.7 1,2-Dimethylenecycloalkane-Magnesium Reagents 1754.8 Synthesis of Fused Carbocycles, β-γ-Unsaturated Ketones, and 3-Cyclopentenols from Conjugated Diene-Magnesium Reagents 1784.9 Synthesis of Spiro-γ-Lactones and Spiro-δ-Lactones from 1,3-Diene-Magnesium Reagents 1844.10 Synthesis of γ-Lactams from Conjugated Diene-Magnesium Reagents 1904.11 Low-Temperature Grignard Chemistry 1924.12 Typical Procedures for Preparation of Active Magnesium and Typical Grignard Reactions as Well as 1,3-Diene Chemistry 1975 Copper 2095.1 Background of Copper and Organocopper Chemistry 2095.2 Development of Rieke Copper 2105.3 Phosphine-Based Copper 2115.4 Lithium 2-Thienylcyanocuprate-Based Copper 2205.5 Copper Cyanide-Based Active Copper 2245.6 Formal Copper Anion Preparation and Resulting Chemistry 2285.7 Typical Experimental Details of Copper Chemistry 2326 Indium 2416.1 Background and Synthesis of Rieke Indium 2416.2 Preparation of Organoindium Compounds 2416.3 Preparation and Reactions of Indium Reformatsky Reagents 2466.4 Experimental Details for Preparation and Reactions of Activated Indium 2507 Nickel 2557.1 Preparation of Rieke Nickel, Characterization of Active Nickel Powder, and Some Chemistry 2557.2 Preparation of 3-Aryl-2-hydroxy-1-propane by Nickel-Mediated Addition of Benzylic Halides to 1,2-Diketones 2617.3 Preparation of 3-Arylpropanenitriles by Nickel-Mediated Reaction of Benzylic Halides with Haloacetonitriles 2657.4 Reformatsky-Type Additions of Haloacetonitriles to Aldehydes Mediated by Metallic Nickel 2677.5 Preparation of Symmetrical 1,3-Diarylpropan-2-ones from Benzylic Halides and Alkyl Oxalyl Chlorides 2697.6 Nickel-Mediated Coupling of Benzylic Halides and Acyl Halides to Yield Benzyl Ketones 2737.7 Nickel-Assisted Room Temperature Generation and Diels–Alder Chemistry of o-Xylylene Intermediates 2758 Manganese 3058.1 Preparation of Rieke Manganese 3058.2 Direct Formation of Aryl-, Alkyl-, and Vinylmanganese Halides Oxidative Addition of the Active Metal to the Corresponding Halide 3068.3 Direct Formation of Organomanganese Tosylates and Mesylates and Some Cross-Coupling Reactions 3168.4 Benzylic Manganese Halides, Sulfonates, and Phosphates: Preparation, Coupling Reactions, and Applications in New Reactions 3208.5 Preparation and Coupling Reactions of Thienylmanganese Halides 3398.6 Synthesis of β-Hydroxy Esters Using Active Manganese 3438.7 Reductive Coupling of Carbonyl-Containing Compounds and Imines Using Reactive Manganese 3478.8 Preparation of Heteroarylmanganese Reagents and Their Cross-Coupling Chemistry 3559 Calcium 3719.1 Preparation of Rieke Calcium 3719.2 Oxidative Addition Reactions of Rieke Calcium with Organic Halides and Some Subsequent Reactions 3729.3 Preparation and Reaction of Calcium Cuprate Reagents 3739.4 Preparation and Reactions of Calcium Metallocycles 3779.5 Synthesis of Polyphenylcarbynes Using Highly Reactive Calcium, Barium, and Strontium: A Precursor for9.6 Chemical Modification of Halogenated Polystyrenes Using Rieke Calcium or Rieke Copper 38610 Barium 39110.1 Preparation of Rieke Barium 39110.2 Oxidative Addition of Rieke Barium to Allylic Halides: Preparation of Stereochemically Homogeneous Allylic Barium Reagents 39211 Iron 39511.1 Preparation of Highly Reactive Iron and Some Oxidative Addition Chemistry 39512 Palladium and Platinum 39912.1 Preparation of Highly Reactive Palladium and Platinum and Some Oxidative Addition Chemistry 39913 Highly Reactive Uranium and Thorium 40713.1 Two Methods for Preparation of Highly Reactive Uranium and Thorium: Use of a Novel Reducing Agent Naphthalene Dianion 40714 Aluminum 42514.1 Preparation of Highly Reactive Aluminum and Reaction with Aryl Halides 42515 Cobalt 42915.1 Two Methods for Preparing Rieke Cobalt: Reaction with CO and Also Fischer–Tropsch Chemistry 42916 Chromium 44316.1 Preparation of Highly Reactive Chromium Metal and Its Reaction with CO to Yield Cr(CO)6 443References 446Index 447