Synthesis of functionalized cyclotriveratrylene analogues with C1-symmetry and the application for 1,4-Michael addition of alcohols to unsaturated aryl ketone

C1-symmetric cyclotriveratrylene analogues 2–8 with various functional groups at one benzene moiety were prepared starting from the selectively demethylated compound 1. Through the chemical resolution, a pair of enantiomers of C1-symmeric compound 1 could be separated with gram scale. Compound 8, which possessed an N-linked imidazolium unit at the upper rim of the macrocyclic skeleton through a methylene linker, was successfully applied to 1,4-Michael addition reaction of alcohol to unsaturated aryl ketone. Its supramolecular catalytic activity as an NHC precursor was demonstrated by the chem-selectivity to aromatic alcohol than alkyl alcohol.