Rate acceleration effects in the Nazarov cyclization of aryl dienones

ORGN 523

Andrew P. Marcus, apmarcus@berkeley.edu, Department of Chemistry, University of California Berkeley, 837 Latimer Hall, Berkeley, CA 94720 and Richmond Sarpong, rsarpong@berkeley.edu, Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720.
An unexpected rate enhancement of the Nazarov cyclization in aryl dienones has been discovered. In electron-rich arene systems, substituents at both the &alpha and &gamma positions of an acyclic dienone have been observed to greatly increase the rate of the Nazarov reaction. Substitution at both the &gamma and &delta positions of the dienone appear to have a similar effect. A simple Huckel molecular orbital (SHMO) picture correlates closely with the observed reactivity and in one case has been shown to predict reactivity.

 

New Reactions and Methodology, Heterocycles and Aromatics, Bioorganic Chemistry
8:00 PM-10:00 PM, Tuesday, 12 September 2006 Moscone Center -- Hall D, Poster

Division of Organic Chemistry

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