Electrophilic Addition of Phenylsulfenyl Chloride to Carbon-Carbon Double Bonds in Pentacyclic and Tetracyclic Cage Enones

Abstract

Reaction of tetracyclo]6.3.0.0^3,7.0^4,11]undec-9-en-5-one (3) and of pentacyclo[9.2.0.0^4,8.0^5,13.0^7,12]tridec-9-en-3-one (4) with PhSCl proceeds via addition across the carbon-carbon double bond with concomitant transannular trapping by C=O of the resulting carbocationic intermediate, thereby affording 5 (50%) and 6 (59%), respectively. The structure of 5 was established unequivocally via application of X-ray crystallographic methods.