Cyclic cinchonidine ∶ acid complexes (1 ∶ 1 and 1 ∶ 2) of the chiral modifier cinchonidine (CD) and an alkenoic acid, tiglic acid, in dichloromethane solvent have been observed by FTIR spectroscopy. Both the OH and the quinuclidine N atom of CD are involved in the hydrogen bond with the acid molecule(s). Such dual-site modifier-reactant interactions play an important role in the enantioselective hydrogenation of alkenoic acids over CD-modified Pd catalysts. The stability of these 1 ∶ 1 and 1 ∶ 2 complexes has been probed by addition of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), a stronger base than CD. DBU builds ion pairs with the acid (with 1 ∶ 1 and 1 ∶ 2 stoichiometry) and a hydrogen bond with the OH of CD. However, despite the large difference in basicity between CD and DBU, 1 ∶ 2 CD ∶ acid complexes can still be detected when more than 0.5 equivalent DBU was added with respect to the acid, at which ratio the enantiomeric excess (ee) drops dramatically. Hence, the molecular structure of CD favours formation of cyclic complexes via a dual-site interaction, which is not possible for DBU ∶ acid complexes, and stabilises 1 ∶ 2 CD ∶ acid species, which are proposed to be responsible for enantiodifferentiation.