Diels-Alder reaction involving an unusual dienophile: Computational and mechanistic study

ORGN 83

Jack R. Waas, jwaas@bethel.edu, Department of Chemistry, Bethel University, 3900 Bethel Drive, St. Paul, MN 55112-6999, Daniel A. Singleton, singleton@mail.chem.tamu.edu, Department of Chemistry, Texas A & M University, College Station, TX 77843, and Jacqueline O. Besinaiz, jbesinaiz@tamuk.edu, Department of Chemistry, Texas A&M University-Kingsville, MSC 161, Kingsville, TX 78363.
The Diels-Alder reaction of 1-vinylcyclohexene with methyl 3-oxocyclopenta-1,4-dienecarboxylate (generated in situ from methyl 2-bromo-3-oxocyclopent-1-enecarboxylate in the presence of triethylamine) proceeds to form the [4+2] adduct, with a single regiochemistry and relative stereochemistry. No [2+4] adduct was observed. These experimental results agree well with the calculated reaction and activation energies (using the B3LYP method with the 6-31G(d) basis set) for all possible stereo- and regiochemical outcomes, trajectory calculations, and observed 13C kinetic isotope effects.

 

Process R&D, Physical Organic Chemistry, Heterocycles, Aromatics, Metal-Mediated Reactions
8:00 PM-10:00 PM, Sunday, March 25, 2007 Hyatt Regency Chicago -- Riverside Center, Poster

Division of Organic Chemistry

The 233rd ACS National Meeting, Chicago, IL, March 25-29, 2007