Chemical transformations of 4,6-dimethyl-2 beta-hydroxy-8-oxo-3,5,7-trioxatetracyclo[7.2.1.0(4,11).0(6,10)]dodecane

Abstract

Reactions of 4,6-dimethyl-2 beta-hydroxy-8-oxo-3,5,7-trioxatetracyclo-[7.2.1.0(4,11).0(6,10)] dodecane 1 with nucleophiles have been studied. Reaction of 1 with alcohols, triethylsilane, allyltrimethylsilane,and methylthiotrirnethylsilane in CH2Cl2 in the presence of TiCl4 gave the substitution products 2, 7a, 7b, and 7c in 80-90% yields. The substitution reaction took place chemoselectively on the hemiacetal group of 1. Reaction of 1 with cyanotrimethylsilane in CH2Cl2 in the presence of TiCl4 gave compound 8 and the rearranged product 9. The structure of 9 was proven by X-ray analysis.