Quantum mechanical investigations of rearrangements of substituted cyclohexyl radicals to cyclopentylmethyl radical

ORGN 89

Jennifer Anne Robbins Luft, jrobbins@chem.ucla.edu1, Fiona Murphy-Kessabi2, and K. N. Houk, houk@chem.ucla.edu1. (1) Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Ave, Los Angeles, CA 90095-1569, (2) Syngenta Crop Protection AG, Schwarzwaldallee 215, CH-4002 Basel, Switzerland
An unexpected rearrangement of a substituted cyclohexyl radical observed experimentally has been investigated using ab initio, density functional (UB3LYP/6-31G(d)//UB3LYP/6-31G(d)) and CBS-RAD computational methods. The origin of the unusual rearrangement is related to substituent effects on radical stabilities. Radical stabilizing substituents α and β to the radical center cause the observed rearrangement to be energetically favored.

 

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