Synthesis and application of the first planar chiral strong bronsted acid organocatalysts

The synthesis of planar chiral strong Bronsted acid organocatalysts derived from [2.2]paracyclophane is described. Resolution was accomplished according to a modified protocol involving pseudo-ortho-substituted [2.2]paracyclophane-based sulfoxides for the synthesis of three new sulfonic acids. The first planar chiral phosphoric acid diester was obtained from the corresponding phenyl-substituted diol derived from enantiopure 4-bromo-12-hydroxy [2.2]paracyclophane. These new classes of catalysts were tested in an enantioselective FriedelCrafts reaction as well as in a direct asymmetric Mannich reaction and gave yields of up to 93% and ee-values of up to 38%. Chirality, 2012. (C) 2012 Wiley Periodicals, Inc.