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Advanced Free Radical Reactions for Organic Synthesis

Hideo Togo

Hardcover, 264 Pages
First Edition, December 2004
ISBN: 0-08-044374-5


Free radical reactions have become increasingly important and a very attractive tool in organic synthesis in the last two decades, due to their powerful, selective, specific, and mild reaction abilities. Advanced Free Radical Reactions for Organic Synthesis reviews information on all types of practical radical reactions, e.g. cyclizations, additions, hydrogen-atom abstractions, decarboxylation reactions. The book usefully provides experimental details for the most important reactions as well as numerous references to the original literature. By covering both the fundamentals and synthetic applications it is therefore suitable for both new and experienced researchers, chemists, biochemists, natural product chemists and graduate students. This title is the definitive guide to radical chemistry for all scientists.

Editorial Review

Reactions with radicals have a reputation for being difficult to control, and for leading to a multitude of side-products. Hideo Togo disproves this misconception in his remarkable new book, "Advanced Free Radical Reactions for Organic Synthesis". This monograph contains many interesting details concerning the properties of radicals, and explains important principles that one can use to predict the selectivity of radical reactions, such as Baldwin’s Rules for ring-closure reactions. The first chapter thus provides an extremely good introduction for everyone who wishes to delve into radical chemistry, particularly advanced students.

The subsequent chapters highlight specific transformations from the current literature. The author has assembled a treasure trove of pertinent literature citations that collectively present an impressive survey of the field, and cover a broad range of accessible chemical reactions. The numerous synthetic procedures scattered throughout the work will prove of enormous benefit. Although they are kept brief, they will readily enhance the attentive reader’s cumulative experimental know-how.

The author has succeeded in presenting many facets of this very interesting area of chemistry in a highly engaging manner. As a result, anyone who wishes to familiarize themselves with the field of radical chemistry should take the time to look through "Advanced Free Radical Reactions for Organic Synthesis".


What are Free Radicals?
General Aspects of Free Radicals. Aspects of free radicals. Types of free radicals. Reaction style of radicals. Orientation in radical additions. Reactivity in radical additions. Reaction patterns of radicals. Generation of radicals. Familiar and Close Radicals in Our Lives. Stable Free Radicals. Physical and Chemical Characteristics of Free Radicals. Orbital interactions between radicals and olefins. Baldwin's rule. Rate constants in radical reactions.

2. Functional Group Conversion
Radical Coupling Reactions. Radical Reduction. Conversion to Hydroxy Group and Other Functional Groups.

3. Intramolecular Radical Cyclizations
Cyclization to Small-Sized Rings. Cyclization onto olefinic group and acetylenic group by sp3 carbon-centered radicals. Cyclization onto Olefinic Group and Aromatic Group by sp2 Carbon-Centered Radicals. Generation of sp carbon-centered radicals. Cyclization onto carbonyl group by sp3 or sp2 carbon-centered radicals and other related cyclizations. Cyclization to Medium-Sized and Large-Sized Rings. Ring Expansions. Cyclization to Spiro Skeleton. Tandem Cyclization to Polycyclic Rings.

4. Intermolecular Radical Addition Reactions
Addition to Olefins. Reductive conditions. Oxidative conditions. Photochemical conditions. Addition-elimination reactions. Allylation Reactions. Addition-Cyclization Reactions. Reactions with Carbon Monoxide. Addition to Acetylenes.

5. Alkylation of Aromatics
Oxidative Conditions. Non-Oxidative Conditions. Photochemical Conditions. Others.

6. Intramolecular Hydrogen-Atom Abstraction
Hydrogen-atom Abstraction by Oxygen-Centered Radicals: Barton Reaction. Hydrogen-atom Abstraction by Nitrogen-Centered Radicals: Hofmann-Loffler-Freytag Reaction. Hydrogen-atom Abstraction by Carbon-Centered Radicals.

7. Synthetic Uses of Free Radicals for Nucleosides and Sugars: Barton-McCombie Reaction

8. Barton Decarboxylation Reaction with N-hydroxy-2-thiopyridone
Reduction. Conversion to Halides. Conversion to Chalcogenides. Conversion to Other Functional Groups. Carbon-Carbon Bond Formation. Intramolecular radical cyclization. Intermolecular coupling reaction. Intermolecular addition reaction. Alkylation of aromatics. Others.

9. Free Radical Reactions with Metal Hydrides

10. Stereochemistry in Free Radical Reactions
Reduction. Carbon-Carbon Bond Formation.

11. Free Radicals Related to Biology
Vitamin B12. Ene-diyne Reactions: Bergman Cyclization. Radical 1,2-Acyloxy Transfer.

12. Free Radicals for Green Chemistry
Design of Free Radical Precursors. Application of Free Radicals to Environmentally Benign Synthesis.