Advanced Free Radical Reactions for Organic Synthesis

1st Edition - January 14, 2004

eBook ISBN:

9 7 8 - 0 - 0 8 - 0 5 2 4 2 5 - 2

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… Read more

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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.

1. 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-Löffler-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