T. Katsushima, R. Yamaguchi, Satoshi Iemura
Nov 1, 1980
Citations
0
Influential Citations
6
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
Oxymercuration of 3,5-dehydronoriceane (1) followed by sodium borohydride reduction gives exclusively endo-3-noriceanol in 80% yield. The trans-1,3-addition organomercury intermediate is isolated as endo-3-acetoxy-exo-5-(chloromercurio)noriceane. Oxidation of 1 with thallium(III) acetate gives three diacetates, exo,exo- and endo,exo-3,5-diacetoxynoriceanes [(9) and (10)] and endo,exo-4,5-diacetoxytetracyclo[5.3.1.02,6.03,9]undecane (11) in a ratio of 6:61:27 in 68% combined yield. The analogous oxidation of 1 with lead(IV) acetate gives 9, 10, and 11 in a ratio of 50:25:25 in 80% combined yield. On the basis of the stereochemistry of the products as well as the products distribution, we propose that 1,3-bridged metal ion intervenes and plays an important role in the oxymetallation reaction of bicyclo[2.1.0]pentane system.