Chemical synthesis using highly reactive metals / Reuben D. Rieke.

Format:

Book

Author/Creator:

Rieke, Reuben D., 1939- author.

Language:

English

Subjects (All):

Organometallic compounds--Synthesis.

Organometallic compounds.

Reactivity (Chemistry).

Physical Description:

1 online resource (483 pages) : illustrations, tables

Edition:

1st ed.

Place of Publication:

Hoboken, New Jersey : Wiley, 2017.

Summary:

Written by the creator of Rieke metals, valuable for chemical reaction methods and efficiency, this groundbreaking book addresses a significant aspect of organic and inorganic chemistry. The author discusses synthetic methods, preparation procedures, chemical reactions, and applications for highly reactive metals and organometallic reagents. • Addresses a new generation of chemistry that goes beyond the standard use of metals and activation • Provides step-by-step guidelines, chemical equations, and experimental descriptions for handling metals including zinc, magnesium, copper, indium, nickel, manganese, calcium, barium, iron, palladium, platinum, uranium, thorium, aluminum, cobalt, and chromium • Uses a unique approach to highlight methods and techniques that make chemical synthesis and activation of Rieke metals more safe and efficient • Discusses novel applications and special topics, such as highly reactive metals for novel organometallic reagents, semiconducting polymers, plastics electronics, photovoltaics, and the Reformatsky reagent

Contents:

Intro

Title Page

Copyright Page

Contents

Preface

Chapter 1 Genesis of Highly Reactive Metals

Chapter 2 General Methods of Preparation and Properties

2.1 General Methods for Preparation of Highly Reactive Metals

2.2 Physical Characteristics of Highly Reactive Metal Powders

2.3 Origin of the Metals' High Reactivity

References

Chapter 3 Zinc

3.1 General Methods for Preparation of Rieke Zinc

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

Typical Preparation of 3-Fluorobenzylzinc Bromide

Typical Preparation of 4-Cyanobutylzinc Bromide

Typical Preparation of 4-Bromophenylzinc Iodide

Typical Preparation of 3-Methyl-2-Pyridlyzinc Bromide

3.3 Reactions of Organozinc Reagents with Acid Chlorides

Typical Generation of Organozinc Halides from Organic Halides and Active Zinc and Their Copper-Mediated Coupling with Acid Chlorides

Synthesis of 4-Methoxy-2′-Thiomethylbenzophenone Using Tetrakis(triphenylphosphine)palladium(0) as Catalyst

Synthesis of Ethyl 7-(3,4-Difluorophenyl)-7-Oxoheptanoate Using Copper Iodide as Catalyst

Cyanide-Based Rieke Zinc

3.4 Reactions of Organozinc Reagents with α,β‐Unsaturated Ketones

Typical Copper-Mediated Conjugate Addition Reaction of Organozinc Halides to α,β-Unsaturated Ketones

3.5 Reactions of Organozinc Reagents with Allylic and Alkynyl Halides

Typical Reaction of Organozinc Halides with Allylic Halides

Preparation of 2,3-Di(p-Cyanobenzyl)-1,3-Butadiene Reaction

3.6 Negishi Cross-Coupling of Vinyl and Aryl Organozinc Halides

Typical Procedure for the Reaction of RZnX with Aryl and Vinyl Halides

Preparation of Aryl Ketones via Ni-Catalyzed Negishi Coupling Reactions

Typical Reaction Procedure

3.7 Intramolecular Cyclizations and Conjugate Additions Mediated by Rieke Zinc.

3.8 The Formation and Chemistry of Secondary and Tertiary Alkylzinc Halides

3.9 Electrophilic Amination of Organozinc Halides

3.10 Reformatsky and Reformatsky-Like Reagents and Their Chemistry

Synthesis of Reformatsky Reagent in THF

Synthesis of Reformatsky Reagent in Diethyl Ether

3.11 Configurationally Stable Organozinc Reagents and Intramolecular Insertion Reactions

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

3.13 Preparation of 5-Substituted-2-Furaldehydes

Results and Discussion

General Procedure for Pd-Catalyzed Cross-Coupling Reactions

3.14 Preparation and Chemistry of 4-Coumarylzinc Bromide

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

Conclusions

Experimental

General

Preparation of 2-Pyridylzinc Bromide (P1)

Preparation of 3-Pyridylzinc Bromide (P7)

General Procedure for Copper-Free Coupling Reactions

Pd-Catalyzed Coupling Reaction with 4-Iodoanisole (10b)

Preparation of Bipyridines

Pd-Catalyzed Coupling Reaction with Haloanilines

Pd-Catalyzed Coupling Reactions with Halophenols

Copper-Catalyzed SN2 Addition Reactions

Pd-Catalyzed Bimolecular Coupling Reactions

Preparation of Quinolinylzinc Reagents and Subsequent Coupling Reactions

3.16 Preparation of Functionalized α-Chloromethyl Ketones

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

The General Procedure for Dissolving Zinc Metal Reduction

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

Competitive Kinetics

Alkyl Bromides

Aryl, Vinyl, Benzyl, and Allyl Bromides

Stereochemical Studies

Radical Detection

Mechanistic Considerations

Two-Electron Mechanisms: SN2

Ate Complex

SN1.

One-Electron Mechanisms

Outer-Sphere Electron Transfer

Inner-Sphere Electron Transfer

Linear-Free Energy Relationships (LFERs)

Synthetic Applications

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

Regiocontrolled Synthesis of Poly(3-Alkylthiophenes) Mediated by Rieke Zinc

Mechanistic Implications of the Polymerizations

Spectroscopic Studies and Other Characterization

NMR Spectroscopy

Conclusion

General Preparation of Regioregular HT Poly(3-Alkylthiophenes) from 2,5-Dibromo-3-Alkylthiophenes: Preparation of Regioregular HT Poly(3-Hexylthiophene) (4b)

General Preparation of Regiorandom Poly(3-Alkylthiophenes) from 2,5-Dibromo-3-Alkylthiophenes: Preparation of Regiorandom Poly(3-Hexylthiophene) (5b)

Chapter 4 Magnesium

4.1 General Background and Mechanistic Details of Grignard Reaction

General Methods of Metal Activation

4.2 General Methods for Preparation of Rieke Magnesium

4.3 Grignard Reagent Formation and Range of Reactivity of Magnesium

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

Cyclizations of (1,4-Diphenyl-2-butene-1,4-diyl)magnesium with α,ω-Alkylene Dihalides

4.5 Regioselectivity of Reaction of Complexes with Electrophiles

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

4.7 1,2-Dimethylenecycloalkane-Magnesium Reagents

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

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

4.10 Synthesis of γ-Lactams from Conjugated Diene‐Magnesium Reagents

4.11 Low-Temperature Grignard Chemistry

Results and Discussion.

Typical Procedure for the Preparation of the Corresponding Grignard Reagents

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

Anhydrous Magnesium Salts

Preparation of Rieke Magnesium Using Potassium or Sodium as Reducing Agent

Preparation of a Grignard Reagent Using Rieke Magnesium Prepared Using Potassium-Potassium Iodide: 1-Norbornanecarboxyl Acid

Preparation of Rieke Magnesium Using Lithium and Naphthalene as an Electron Carrier

Chemistry of (2-Butene-1,4-diyl)magnesium: Preparation of Activated Magnesium (Mg*)

Typical Cyclization of (1,4-Diphenyl-2-butene-1,4-diyl)magnesium

Typical Reaction of (2,3-Dimethyl-2-butene-1,4-diyl)magnesium

Typical Stepwise Reaction of (2,3-Dimethyl-2-butene-1,4-diyl)magnesium

Typical Regioselective Reaction of Unsymmetrical (2-Butene-1,4-diyl)magnesium

Typical Reaction of Unsymmetrical (2-Butene-1,4-diyl)magnesium with SiCl4

Typical Reaction with 1,2-Dimethylenecyclohexane

Chapter 5 Copper

5.1 Background of Copper and Organocopper Chemistry

5.2 Development of Rieke Copper

5.3 Phosphine-Based Copper

5.4 Lithium 2-Thienylcyanocuprate-Based Copper

5.5 Copper Cyanide-Based Active Copper

5.6 Formal Copper Anion Preparation and Resulting Chemistry

5.7 Typical Experimental Details of Copper Chemistry

Active Copper from CuI and K

Reaction of K-Generated Copper with Pentafluorophenyl Iodide

Preparation of Phosphine-Based Copper

Phosphine-Based Copper Chemistry

Typical Reaction with Acid Chlorides to Form Ketones

Typical 1,4-Addition Reaction with 2-Cyclohexene-1-One

Typical Procedure for Intermolecular Epoxide-Opening Reaction

Typical Procedure for Intramolecular Epoxide-Opening Reaction

Lithium 2-Thienylcyanocuprate-Based Copper and Chemistry.

Preparation of Thienyl-Based Activated Copper

Reaction of Organocopper Reagent with Acid Chlorides

Epoxide Opening of Organocopper Reagent with 1,2-Epoxybutane

Copper Cyanide-Based Active Copper and Chemistry

Preparation of Active Copper and Reaction with Organic Halides to Yield Organocopper Reagents

Cross-Coupling of Benzoyl Chloride with Organocopper Reagents Derived from CuCN∙2LiBr-Based Active Copper

Conjugate Additions with Organocopper Reagents Derived from CuCN∙2LiBr-Based Active Copper

Reaction of Allyl Organocopper Reagents Derived from CuCN∙2LiBr with Benzoyl Chloride

Preparation of Copper Anions and Some Resulting Chemistry

Preparation of Cu(−1)Li(+)

Chapter 6 Indium

6.1 Background and Synthesis of Rieke Indium

6.2 Preparation of Organoindium Compounds

The Direct Synthesis of Diphenylindium Iodide and Ditolyindium Iodide from Activated Indium and Aryl Iodides

6.3 Preparation and Reactions of Indium Reformatsky Reagents

6.4 Experimental Details for Preparation and Reactions of Activated Indium

Preparation of Active Indium and Reaction with Alkyl Iodides

Reaction of Active Indium with Iodine

Triphenylindium

Tritolylindium

Trimethylindium

The Reaction of Activated Indium with Iodobenzene

The Reaction of Activated Indium with Iodotoluene

The Reaction of Triphenylindium with Iodine

Materials

Indium Reformatsky Reaction

Chapter 7 Nickel

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

Preparation of Rieke Nickel Slurries

Surface Analysis

Discussion

Reactions of Slurries

Summary

Experimental Procedures

Preparation of a Typical Nickel Slurry

Preparation of Ni(C6F5)2[P(C2H5)3]2

Preparation of Ni(C6F5)2(C5H5N)2.

Preparation of Ni(C6F5)2[(C6H5)2 PH]2∙C6H5CH3.

Notes:

Includes bibliographical references at the end of each chapters and index.

Description based on print version record.

ISBN:

9781118929131

1118929136

9781523110094

1523110090

9781118929124

1118929128

OCLC:

969640083