Inter- and intramolecular, homo- and cross-coupling radical reactions: Diastereoselectivity introduced by a transition metal cluster

ORGN 274

Gagik Melikyan, gagik.melikyan@csun.edu, Aaron Rowe, Arthur Floruti, Christopher Wild, cw3001@csun.edu, Lucin Devletyan, Nenuphar Nezami, Louis Carlson, Yasuko Hirakawa, and Norman Dean. Department of Chemistry and Biochemistry, California State University Northridge, 18111 Nordhoff str, Northridge, CA 91330
The stereocontrol in radical reactions remains one of the major research thrusts in modern synthetic chemistry. Among the most promising innovative strategies is the coordination of organic radicals with transition metals that moderates the behavior of transient radical species, otherwise unruly. Novel synthetic strategies – Zn-mediated/two-step, THF-mediated/one-step, triflic anhydride-mediated/ one-step, spontaneous/two-step – were successfully applied for the generation of dicobalthexacarbonyl-complexed propargyl radicals and stereoselective assembling of topologically diverse D,L-3,4-diaryl-1,5-alkadiynes and D,L-1,5-cycloalkadiynes. The results of the mechanistic study on the THF-mediated coupling reaction, intramolecular cyclization of bis-propargyl alcohols, and intermolecular cross-coupling of cobalt-complexed propargyl radicals will be presented. The relevance of the project to breast cancer research, in particular, the ability of selected compounds to interfere with estrogen synthesis will also be discussed.
 

Metal-Mediated Reactions and Syntheses
8:00 AM-12:00 PM, Monday, 11 September 2006 Moscone Center -- Room 133, Oral

Division of Organic Chemistry

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