T. Katsushima, R. Yamaguchi, M. Kawanisi
Nov 1, 1980
Citations
0
Influential Citations
4
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
Treatment of 3,5-dehydronoriceane (1) with a catalytic amount of silver tetrafluoroborate results in a novel skeletal rearrangement to afford tetracyclo[5.3.1.02,6.03,9]undec-4-ene (2,4-ethenonoradamantane) (5) in 85% yield. Empirical force-filed calculations suggest that there is no substantial difference in strain energies between 1 and bicyclo[2.1.0]pentane which is inert toward silver(I) ion. Acetolysis of endo-3-noricyl (endo-tetracyclo[5.3.1.02,6.04,9]undec-3-yl) tosylate (7) gives exo-3-acetoxynoriceane (exo-3-acetoxytetracyclo[5.3.1.02,6.04,9]undecane) (11), exo-4-acetoxytetracyclo[5.3.1.02,6.03,9]undecane (12), and 5 in a ratio of 36:42:22. Similar acetolysis of the exo-isomer of 7 gives the same products but in a different ratio (11:12:5=9:47:44). A stepwise carbocation mechanism is proposed for the above mentioned silver(I) ion-catalyzed rearrangement.