Mapping the Binding Motifs of Deprotonated Monounsaturated Fatty Acids and Their Corresponding Methyl Esters within Supramolecular Capsules.

Abstract

A suite of NMR techniques revealed that a cavitand (1) formed 2:1 host-guest complexes with a range of monounsaturated fatty carboxylates and their corresponding methyl esters. All of the carboxylates bound to the capsule in a J-shaped motif with the carboxylate at the equatorial region of the dimeric capsule, and the reverse turn of the chain and the methyl terminal in each polar region of the host. Guest exchange was slow on the NMR time scale, while tumbling was slow or close to the NMR time scale depending on the position and stereochemistry of the double bond. In contrast, the methyl esters were found to bind in three motifs depending on the position and stereochemistry of the double bond. Thus, the esters were observed to bind in a J-shaped, U-shaped (the turn in the guest occupying a polar region and the two termini competing for occupancy of the other pole), or a reverse J-shaped motif (ester moiety and turn each occupying a pole and the methyl terminal located near the equator). Relative binding constant (Krel) determinations revealed that the affinity for the capsule was dependent on the position and stereochemistry of the double bond.