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Organic Pedagogical Electronic
Network
Radical Reactions in
Biological Systems
Created by Rowan Arave and Alexandra Butler
Edited by Margaret Hilton
Honors Organic Chemistry
CHEM 2321 (Sigman), 2013
Radical Organic Chemistry
Wiki Page: http://en.wikipedia.org/wiki/Radical_(chemistry)
Overview: Free Radicals are atoms without a full set of valence
electrons. This causes the outer electron shell to be ‘open’, and thus,
more reactive. Radical reactions take place in a series of three steps:
initiation, propagation, and termination.
Mechanism Initiation
Propagation
Termination
Radical Organic Chemistry
Wiki Page: http://en.wikipedia.org/wiki/Radical_(chemistry)
Overview: Free Radicals are atoms without a full set of valence
electrons. This causes the outer electron shell to be ‘open’, and thus,
more reactive. Radical reactions take place in a series of three steps:
initiation, propagation, and termination.
Early Examples
Moses Gomberg discovered the first
free radical, a Triphenyl Methyl
Radical, in 1900.
Friedrich Paneth pioneered free
radical decomposition in organic
compounds. In 1929 he discovered
the free methyl radical.
Synthesis and Repair of DNA
M. Kolbergr et al. / Biochimica et Biophysica Acta 1699 (2004) 1–34
The reduction of ribonucleotides to deoxyribonucleotides (RNA  DNA) is the result of a radical
reaction. Ribonucleotide reductase (RNR) is an enzyme that helps to catalyze this
transformation. The reduction of RNA to DNA is the rate limiting step in synthesis of DNA.
Therefore, this reaction plays a large part in cell growth and maintenance.
Problems
1.The Journal of Organic Chemistry DOI: 10.1021/jo4001433
2. Modern physical organic chemistry
3. Smith pg. 557
1. Lipid peroxidation occurs due to oxidative stress.
Polyunsaturated fatty acids and sterols undergo
radical chain oxidation to complete this process.
Draw an arrow-pushing mechanism for the following
reaction of triphenylmethyl radical with molecular
oxygen.
2. The trityl radical is in equilibrium with an
unsymmetrical dimer (note: not Ph3C-CPh3). Propose
a mechanism for the formation of this unsymmetrical
dimer.
3. BHT (butylated hydroxy toluene) is a synthetic
anti-oxidant that interrupts radical chain reactions.
Propose a mechanism for how this could occur and
predict the resulting products. (Hint: think resonance)
BHT
This work is licensed under a
Creative Commons Attribution-
ShareAlike 4.0 International
License.
Contributed by:
Created by Rowan Arave and Alexandra Butler (Undergraduates)
Edited by Margaret Hilton
Honors Organic Chemistry
CHEM 2321 (Sigman),
University of Utah
2013

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Radical reactions in biological systems

  • 1. Organic Pedagogical Electronic Network Radical Reactions in Biological Systems Created by Rowan Arave and Alexandra Butler Edited by Margaret Hilton Honors Organic Chemistry CHEM 2321 (Sigman), 2013
  • 2. Radical Organic Chemistry Wiki Page: http://en.wikipedia.org/wiki/Radical_(chemistry) Overview: Free Radicals are atoms without a full set of valence electrons. This causes the outer electron shell to be ‘open’, and thus, more reactive. Radical reactions take place in a series of three steps: initiation, propagation, and termination. Mechanism Initiation Propagation Termination
  • 3. Radical Organic Chemistry Wiki Page: http://en.wikipedia.org/wiki/Radical_(chemistry) Overview: Free Radicals are atoms without a full set of valence electrons. This causes the outer electron shell to be ‘open’, and thus, more reactive. Radical reactions take place in a series of three steps: initiation, propagation, and termination. Early Examples Moses Gomberg discovered the first free radical, a Triphenyl Methyl Radical, in 1900. Friedrich Paneth pioneered free radical decomposition in organic compounds. In 1929 he discovered the free methyl radical.
  • 4. Synthesis and Repair of DNA M. Kolbergr et al. / Biochimica et Biophysica Acta 1699 (2004) 1–34 The reduction of ribonucleotides to deoxyribonucleotides (RNA  DNA) is the result of a radical reaction. Ribonucleotide reductase (RNR) is an enzyme that helps to catalyze this transformation. The reduction of RNA to DNA is the rate limiting step in synthesis of DNA. Therefore, this reaction plays a large part in cell growth and maintenance.
  • 5. Problems 1.The Journal of Organic Chemistry DOI: 10.1021/jo4001433 2. Modern physical organic chemistry 3. Smith pg. 557 1. Lipid peroxidation occurs due to oxidative stress. Polyunsaturated fatty acids and sterols undergo radical chain oxidation to complete this process. Draw an arrow-pushing mechanism for the following reaction of triphenylmethyl radical with molecular oxygen. 2. The trityl radical is in equilibrium with an unsymmetrical dimer (note: not Ph3C-CPh3). Propose a mechanism for the formation of this unsymmetrical dimer. 3. BHT (butylated hydroxy toluene) is a synthetic anti-oxidant that interrupts radical chain reactions. Propose a mechanism for how this could occur and predict the resulting products. (Hint: think resonance) BHT
  • 6. This work is licensed under a Creative Commons Attribution- ShareAlike 4.0 International License. Contributed by: Created by Rowan Arave and Alexandra Butler (Undergraduates) Edited by Margaret Hilton Honors Organic Chemistry CHEM 2321 (Sigman), University of Utah 2013