Discovery of a bifunctional macrocycle: Guest dependent reactivity

ORGN 81

Jeremiah J. Gassensmith, jgassens@nd.edu, Department of Chemistry and Biochemistry and Walther Cancer Research Center, University of Notre Dame, Notre Dame, IN 46556 and Bradley D Smith, Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556.
Recently we discovered that a macrocyclic amine can attack primary haloalkanes with unprecedented reactivity to give N-alkylated salts. The accelerated reaction is due to formal enzyme-like properties such as pre-reaction complexation and enhancement of leaving group ability by hydrogen bonding with the NH residues in the macrocyclic cavity. Here we report that the enhanced reactivity turns to elimination when the substrate has relatively acidic CH residues. Structural and mechanistic studies will be presented that explain the remarkable reaction of this structurally simple amine.

 

Physical Organic Chemistry: Calculations, Mechanisms, Photochemistry, and High-Energy Species
1:00 PM-5:20 PM, Sunday, 10 September 2006 Moscone Center -- Room 133, Oral

Division of Organic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006