Tris-annelated benzenes selectively perfunctionalized on one side only: hexachlorobenzotrinorbornadiene as a versatile scaffold for the construction of molecular domes

Well-defined. rigid molecular domes are obtained via Substitution of the chlorine atoms of hexachlorobenzotrinorbornadiene syn-3. efficiently synthesized in 1:2 ratio along with its anti-isomer by CuTC-promoted cyclotrimerization of 3-bromo-2-trimethylstannylnorbornadiene 8. The three dichlorovinyl functions at the edge of syn-3 are displaced by sulfur nucleophiles and Grignard reagents with Ni(II)Cl(2)dppe as catalyst, gaining the persubstituted vinyl sulfides 9 and 10, and persubstituted methyl 12 and phenylethynyl 13.