Stereochemistry of radical-pair recombinations during photo-Fries reactions in confining media

ORGN 310

Jinqi Xu and Richard G. Weiss. Department of Chemistry, Georgetown University, 37th and O Streets, NW, Washington, DC 20057

The stereochemical fates of both photo-Fries and decarbonylated photoproducts of 1-naphthyl (R)-2-phenylpropanoate (R-BzEN) have been investigated in polymeric films and isotropic liquids. Up to 24% ee in the decarbonylated photoproducts (BzON, 2BN, and 4BN) and significant racemization of the photo-Fries product 2AN (but not 4AN) are found when the reaction is conducted in polymeric films. The course of radical-pair recombinations is affected by the degree of polymer crystallinity and film stretching. These results and the bizarre dependence of the ee on temperature will be discussed on the bases of the natures of the reaction cavities and the mechanisms by which the products are formed.

 

Materials, Devices, and Switches
8:00 AM-11:20 AM, Tuesday, September 9, 2003 Sheraton New York -- Versailles Ballroom, Oral

Division of Organic Chemistry
The 226th ACS National Meeting, New York, NY, September 7-11, 2003