Calix[4]resorcarenes as chiral NMR discriminating agents

ORGN 681

Courtney M O'Farrell, cofarrel@bates.edu, Department of Chemistry, Bates College, Lewiston, ME 04240 and Thomas J. Wenzel, twenzel@bates.edu, Chemistry, Bates College, Lewiston, ME 04240.
Tetra hydroxy-prolinylmethyl derivatives of a tetra-sulfonated calix[4]resorcarene are effective chiral NMR solvating agents for water-soluble compounds with phenol, pyridyl, or naphthyl rings. The aromatic compounds form host-guest complexes with the calix[4]resorcarenes in water. Complexation of substrates with the calix[4]resorcarenes are likely promoted by hydrophobic effects. Aromatic resonances of the substrates show substantial upfield shifts because of shielding from the aromatic rings of the calix[4]resorcarene, and several resonances in the H-1 NMR spectra typically exhibit enantiomeric discrimination. The extent of enantiomeric discrimination depends in part on interactions of the substituent groups of the substrates with the hydroxy-prolinylmethyl groups of the calix[4]resorcarenes. The effectiveness of a calix[4]resorcarene prepared from cis-4-hydroxy-D-proline, cis-4-hydroxy-L-proline and trans-4-hydroxy-L-proline as a chiral NMR discriminating agents are compared to the L-prolinylmethyl derivative.