Chemistry 246H: Organic Free Radical Chemistry
Fall 2001
Tuesday/ Thursday 12:00-1:45 pm, Social Sciences 1 room 149

Instructor:
Office:
Office Hours:
Professor Rebecca Braslau (braslau@chemistry.ucsc.edu)
Thimann 337, tel. 459-3087
Wednesdays, 1:30-3:30 pm

Prerequisite: successful completion of Chem 143, or Chem 240E or Chem 240F, or consent of instructor.

Student performance will be evaluated by a (100 points), a (200 points) and a (100 points): , with final exam.

Tentative Course Syllabus:

  • Thermodynamics of Organic Free Radicals
    • Radical Stabilization, Bond Dissociation Energies
    • Resonance and Electronic Stabilization
  • Kinetics of Organic Free Radicals
    • Rate Constants of Radical Processes
    • "Radical Clocks"
    • Persistent Radicals
  • Initiators to Generate Free Radicals
  • Free Radical Chain Reactions
    • Tin Hydride Based Methodologies
    • The Barton Method
    • SH2 Reactions
      • Atom (and Group) Transfer
      • Hydrogen Translocation
      • Free Radical Halogenation
  • Stochiometric Free Radical Reactions
    • Metal Based Reactions: SmI2 , Ni, Co, MnIII, CeIV, O-Stannyl Ketyl
    • Non-metal Redox: SET, PET, and Electrochemistry,
    • Photoexcitation to form biradicals
    • photodeprotection
  • Radical Rearrangements
  • Control of Stereochemistry in Radical Reactions
    • Control of Relative Stereochemistry
      • Beckwith Transition State
      • 1,2 diastereoselectivity
    • Control of Absolute Stereochemistry
      • Chiral Auxiliaries
      • Optically Active Lewis Acids
  • Free Radical Polymerization
    • Uncontrolled
    • Living Free Radical Polymerization
      • Nitroxide-mediated
      • ATRP
      • RAFT
  • Free Radicals in Biology
    • Bergman Diradicals
    • Radical Damage to DNA
    • Amino Acid Radicals
      • Protein free radicals in enzyme active sites
      • Role in aging and Alzheimer’s

There will be no single text for the class: the bulk of the material covered will come from the scientific literature. In addition, the following texts are recommended as reference material:

P. Renaud and M. Sibi, Ed. "Radicals in Organic Synthesis" (2 volume set), Wiley-VCH, Weinheim, 2001.
M. J. Perkins "Radical Chemistry" Ellis, Horwood, New York, 1994.
B. Giese "Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds" Pergamon, Oxford, 1986.
D. P. Curran, N. A. Porter, B. Giese, "Stereochemistry of Radical Reactions," VCH, Weinheim, 1996.