S. Uemura, H. Miyoshi, M. Okano
Jan 23, 1979
Citations
0
Influential Citations
14
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract Treatment of norbornene, norbornadiene, benzonorbornadiene, and chloro- and methoxy-benzonorbornadiene with thallium(III) acetate in methanol affords only the corresponding cis - exo -acetoxythallation adducts in a sharp contrast to oxymercuration of such strained olefins where methoxymercuration prevails. In the cases of substituted benzonorbornadienes the products are obtained as the regioisomeric mixtures, the isomer ratio being determined by 13 C NMR. In the cases of 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2-methyl-2,3-dicarboxylic anhydride, and 5-norbornen-2- endo -carboxylic acid, lactonization occurs to give a trans -oxythallation adduct having a lactone ring, no introduction of either methoxy or acetoxy groups being observed. 1 H and/or 13 C NMR data for several new oxythallation adducts are provided. The alkaline sodium borohydride reduction of adducts in methanol affords mainly the parent olefin together with 10–16% yields of the corresponding exo -alcohol.