Quantum chemical calculations have successfully predicted the stereoselectivities of many BINOL phosphoric acid catalyzed reactions over the past 10-15 years. Herein we report a contrasting example: a reaction for which standard quantum chemistry techniques have proven unexpectedly ineffective at explaining the stereoselectivity. The Nazarov cyclizations of a divinyl ketone catalyzed by a BINOL phosphoric acid or H8-BINOL dithiophosphoric acid were studied with a conventional contemporary quantum chemical approach, consisting of transition state optimizations with B3LYP-D3(BJ) and single-point calculations with several functionals in implicit solvent. Unexpectedly, different functionals gave widely different predictions of the level of enantioselectivity and were unable even to agree on which enantiomer of the product would predominate. Molecular dynamics simulations with the OPLS-AA force field provided evidence that the transition state geometries optimized with DFT in the gas phase or in implicit solvent are not good representations of the true transition states of these reactions in solution. One possible reason for this, which may also explain the failure of quantum chemical techniques to reliably predict the enantioselectivity, is the fact that the transition states contain ion pairs which are not highly organized and do not contain any strongly directional noncovalent interactions between the substrate and the catalyst.