Activated Metals in Organic Synthesis

✍ Scribed by P. Cintas (Author)

• Publisher: CRC Press
• Year: 1993
• Leaves: 247
• Edition: 1
• Category: Library

✦ Synopsis

Activated Metals in Organic Synthesis discusses fundamental principles of the generation of activated, highly reactive metals, and their applications in organic synthesis. Following an introductory chapter on basic forms of metals the chapters in Part 1 are devoted to common strategies utilized for the preparation of active metals. These strategies include vaporization and subsequent co-condensation of metal atoms, in addition to depassivating methods employed commonly in laboratory syntheses. Chapters in Part 2 discuss relevant organic transformations in which metal activation plays a crucial role. Specific topics covered include metal-induced reductive methods; pinacolic, Reformatsky-, and Barbier-type reactions; McMurry ketone-olefin coupling; and the Bernet-Vasella reaction. Each chapter is followed by literature citations ranging from specific references to significant reviews. Many structural formulas are provided, making it easy to follow each synthesis. The book will be an important reference for students, organic chemists, and researchers in all areas of organometallic chemistry.

✦ Table of Contents

PART ONE: METAL ACTIVATION, I. BASIC FORMS OF METALS, A. MASSIVE METALS, B. DISPERSED METALS, 1. Metal Films, 2. Metal Powders, 3. Organometallic Powders, 4. Other Dispersed Forms, II. METAL VAPOR CHEMISTRY, A. GENERAL CONSIDERATIONS, B. ALKALI AND ALKALINE-EARTH METAL VAPORS, C. TRANSITION METAL VAPORS, D. METAL ATOM-SOLVENT CONDENSATIONS, E. OTHER APPLICATIONS, III. DEPASSIVATING METHODS, A. ACTIVATION BY REAGENTS AND SOLVENTS, B. RIEKE METALS, C. METAL ANTHRACENE/NAPHTHALENIDE, D. OTHER REDUCING METHODS, E. INTERMETALLIC COUPLES, F. ULTRASONIC IRRADIATION, 1. Sonochemistry. Basic Principles, 2. Reactions on Metal Surfaces, 3. Reactive Metal Powders, 4. Organometallic Compounds, G. METAL GRAPHITES, 1. Introduction, 2. Structural Considerations, 3. Graphite Intercalation Compounds, 4. Metal Dispersions on Graphite Surfaces, 5. Other Metallic Graphite Compounds, PART TWO: METAL-MEDIATED REACTIONS IV. REDUCTIONS, A. UNSATURATED SYSTEMS, 1. Alkenes, Alkynes, and Aromatic Systems, 2. Carbonyl Substrates, 3. Conjugated Reduction, B. ORGANIC HALIDES AND RELATED SYSTEMS, C. DEOXYGENATION REACTIONS, D. REDUCTION OF NITROGEN AND SULFUR, FUNCTIONAL GROUPS, REDUCTIVE CARBONYL COUPLING REACTIONS, A. PINACOL REACTION, 1. Classical Methods, 2. Low-Valent Metal Reagents, 3. Other Metal-mediated Pinacolic Reactions, B. McMURRY-TYPE REACTIONS, 1. Titanium Reagents, 2. Scope and Limitations, 3. McMurry Coupling with Metals other than Titanium, VI. ADDITION REACTIONS TO CARBONYL COMPOUNDS, A. BARBIER-TYPE REACTIONS, 1. Introduction, 2. Activated Metals, 3. Reactions in Aqueous Media, B. REFORMATSKY-TYPE REACTIONS, 1. Introduction, 2. The Reformatsky Reagent, 3. The Role of Zinc Activation, 4. Metals other than Zinc, 5. Stereoselective Reformatsky Reactions, VII. CYCLIZATIONS, A. SIMMONS-SMITH-TYPE REACTIONS, 1. Introduction, 2. Simmons-Smith Reagents, 3. Metals other than Zinc, B. CYCLOADDITIONS, C. REFORMATSKY-TYPE CYCLIZATIONS, 1. Dreiding-Schmidt Reactions, 2. Intramolecular Reactions, 3. Other Zinc-mediated Cyclizations, D. MISCELLANEOUS CYCLIZATIONS, VIII. THE BERNET-VASELLA REACTION, A. INTRODUCTION, B. ZINC REAGENTS, C. SYNTHETIC APPLICATIONS, Index

✦ Subjects

Physical Sciences;Chemistry;Organic Chemistry;Physical Chemistry