New Functionalized Derivatives of Sulfur- and Oxygen-Containing Hexacyclic Cage Compounds

Several new sulfur- and oxygen-bridged hexacyclic cage compounds have been obtained via transannular cyclization of pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione (1). Thus, cage-annulated thiapodands 9 and 10 were prepared via reaction of ditosylate 6 with 2-mercaptoethylamine (7) or 2-mercaptoethanol (8), respectively. Other ditosylate 11 was reacted with thiourea to afford the corresponding dimercapto podand 12. An optically active podand (R,R)-14 was prepared in similar fashion by reacting ditosylate 6 with (R)-2-amino-1-butanol (R)-(13). Functionalized 4-thiahexacyclo[ 5.4.1.0.02,6.03,10 .05,9.08,11]dodecanes 17a-band18a-b were prepared via reactions of 1 with 2-chloro- (15) or 2-bromoethanol (16), respectively in the presence of H2S(g) and HCl(g). The corresponding reaction of 1 with 2 equivalents of 8 produced the corresponding bisthioacetal 20, which subsequently was changed into a spiro-cage-annulated dithiacrown ether 22.