Planar chiral PHANOLs as double hydrogen bonding donor organocatalysts: Synthesis and catalysis

4,12-Dihydroxy[2.2]paracyclophanediol (PHANOL; 1), and its para-substituted derivatives 2, 5 and 7, were found to catalyse Diels-Alder cycloadditions of alpha,beta-unsaturated aldehydes or ketones with dienes and/or epoxide ring opening reactions with amines. The mode of catalysis by the PHANOLs is via double hydrogen bonding to the two sp(2) lone pairs of a carbonyl group or the two lone pairs of the epoxide. The order of activity of the PHANOLs for catalysis of the Diels-Alder reaction essentially correlates with the expected hydrogen-bond donor strength based on the degree of electron-withdrawing capability of the group(s) in the para position. In contrast, ortho-substituted PHANOLs 10, 11 and 14 were not active as catalysts due to steric interference with the double hydrogen bonding mode. H-1 NMR and IR spectral data for the various PHANOLs are discussed in support of the proposed double hydrogen bond mode.