Silver(I)-Catalyzed Isomerization of Water-Soluble Quadricyclanes

Article abstract of DOI:10.1021/jo00227a004

In aqueous ammonia, silver(I)-catalyzed isomerization of quadricyclanes to norbornadienes was investigated.The catalytic action of silver(I) perchlorate induced rapid and clean isomerization of water-soluble quadricyclanes 1b-g to the corresponding norbornadienes 2b-g even at room temperature.In the isomerization, the silver(I) catalyst might attack 1 from the five-membered ring, which was different from the directions observed in the cobalt(II)-porphyryn- and rhodium(I)-catalyzed reactions.The present reactions proceed via the formation of the cationic species and the successive cleavage of the highly strained cyclopropane ring of 1 to give 2.