The reaction of tryptamine and (2-oxo-cyclohexyl)-acetic acid can be catalyzed by 3,3'-Bis(triphenylsilyl)-1,1'-bi-2-naphthol phosphoric acid to give an asymmetric beta-carboline. This reaction was first studied by Holloway et al. but their mechanistic work did not explain the high stereoselectivity achieved. This study uses density functional theory and hybrid quantum mechanics/molecular mechanics calculations to investigate this reaction and provide a model to explain its outcome. The step leading to diastereo- and enantioselectivity is an asymmetric Pictet-Spengler reaction involving an N-acyliminium ion bound to the catalyst in a bidentate fashion. This interaction occurs via hydrogen bonds between the two terminal oxygen atoms of the catalyst phosphate group and the hydrogen atoms at N and C2 of the substrate indole group. These bonds hold the transition structure rigidly and thus allow the catalyst triphenylsilyl groups to influence the enantioselectivity.