Radical Reactions
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Radical Reactions

Author(s):
Publication Date:
March 31, 2023
Copyright © 2023 American Chemical Society
eISBN:
‍9780841299702
DOI:
10.1021/acsinfocus.7e7001
Read Time:
four to five hours
Collection:
2
Publisher:
American Chemical Society
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Radical Reactions provides the reader a brief overview of radical reactions, an overview overlooked in most undergraduate chemistry curriculums. Most of the exciting developments in the field of radical and radical ion chemistry came about because someone understood the fundamentals and was able to design new chemistry based upon that understanding. The target audience is individuals who have had at least one semester of organic chemistry.

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Detailed Table of Contents
About the Series
Preface
Chapter 1
The Structure, Energetics, and Reactivity of Carbon-Centered Radicals
1.1
Overview
1.2
σ- and π-Radicals
1.3
Stabilization of Radicals
1.3.1
C–H Bond Strengths as a Measure of Stability
1.3.2
Hyperconjugation
1.3.3
Conjugation and Resonance
1.3.4
Effect of Hybridization
1.3.5
Effect of an Adjacent Radical Center on C–H Bonds
1.4
Elementary Reactions Involving Radicals
1.4.1
Free Radical Chain Reactions
1.4.2
Atom Transfer
1.4.3
Addition
1.4.4
Fragmentation (β-Cleavage)
1.4.5
Radical–Radical Reactions (Combination/Disproportionation)
1.4.6
Generation of Free Radicals
1.5
Free Radical Halogenation
1.6
Chapter Summary
1.7
That’s a Wrap
Chapter 2
Radical Ions: Structure, Energetics, and Reactivity
2.1
Overview
2.2
Generation of Radical Ions through Electron Transfer
2.3
Structure of Radical Ions
2.4
Reactions Following (or Occurring Concurrently with) Single-Electron Transfer
2.4.1
Dissociative Electron Transfer
2.4.2
Acid/Base Chemistry
2.4.3
Two-Electron Chemistry
2.4.4
Rearrangements and Electron Transfer Probes
2.5
Chapter Summary
2.6
That’s a Wrap
2.7
Insider Q&A: Jason Gillmore
Chapter 3
Oxidation at the Interface of Chemistry, Biology, and Materials Science
3.1
Overview
3.2
The Electronic Structure of Molecular Oxygen
3.3
The Combustion of Hydrocarbons: A Free Radical Explosion Process
3.4
Autoxidation
3.5
Key Reactions Related to Autoxidation
3.6
Lipid Peroxidation, DNA/Protein Oxidation, and Oxidative Stress
3.7
Antioxidants: Fundamental Principles and Examples
3.8
Chapter Summary
3.9
That’s a Wrap
Chapter 4
Radicals in Organic Synthesis
4.1
Overview
4.2
Radical Initiators
4.3
Additions to Alkenes
4.4
Single-Electron Transfer
4.5
Cyclizations
4.6
Rearrangements
4.7
Cascade Reactions
4.8
Photoredox Catalysis
4.9
Chapter Summary
4.10
That’s a Wrap
4.11
Insider Q&A: Marc Robert
Chapter 5
Radical Polymerizations
5.1
Overview
5.2
Traditional Radical Polymerizations
5.3
The Persistent Radical Effect
5.4
Controlled Radical Polymerizations
5.4.1
Nitroxyl Radical Mediated Polymerizations
5.4.2
Cu(I)-Based Methods: Atom Transfer Radical Polymerizations (ATRP)
5.4.3
Reversible Addition/Fragmentation Chain Transfer (RAFT) Polymerizations
5.5
Chapter Summary
5.6
That’s a Wrap
Chapter 6
Enzyme-Catalyzed Reactions Involving Radicals and Single-Electron Transfer
6.1
Overview
6.2
What Are Enzymes?
6.3
Oxidases
6.3.1
Cytochrome P450
6.3.2
Galactose Oxidase
6.3.3
Case Study: Monoamine Oxidase
6.4
DNA Photolyase
6.5
Chapter Summary
6.6
That’s a Wrap
Bibliography
Glossary
Index
Reviewer quotes
Richard Spinney, The Department of Chemistry & Biochemistry, The Ohio State University
This will be a great introduction to free radical chemistry for graduate or senior undergraduate students pursuing research in the area.
Chujun Zhou, Graduate Student, University of Arkansas
The style is straightforward and easy to follow.
Author Info
Nathan Price
Nathan Price is a doctoral candidate in the Department of Chemistry at Virginia Tech with Prof. J. M. Tanko. He received his B.S. in Chemistry from Roanoke College in 2019. His research interests include mechanism discovery and the characterization of radical intermediates. He is currently working on the development of a novel single electron transfer mechanism for the reaction of monoamine oxidase with substrates related to 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP).
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J. M. (Jim) Tanko
J. M. (Jim) Tanko is a Professor in the Department of Chemistry at Virginia Tech. He received his B.A. in Chemistry from UMBC, Ph.D. at Iowa State with Prof. Glen A. Russell, and was a postdoctoral researcher at Penn State with Prof. Philip S. Skell. His research interests involve electrochemical studies addressing the mechanism and kinetics of radical ion rearrangements and nanosecond laser flash photolysis to measure rate constants of reactions involving oxygen-centered radicals. Most recently, his group has turned its attention to the mechanism of the monoamine oxidase catalyzed oxidations of compounds related to the neurotoxin MPTP.
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