Modeling of kinetics, stereo-, regio-and enantioselectivity of reactions representing different typical cases of multiphase heterogeneous organic catalysis is usually discussed within the framework of ideal surfaces, neglecting the polyatomic nature of reacting molecules. However, there is a number of cases when the real adsorption geometry of large organic molecules, especially in catalysis on nanoparticles, should be accounted for. Particularly challenging is the description of selectivity as a function of conversion when conventional models often fail to capture experimental behavior. Data on chemoselective hydrogenation of α,β-unsaturated aldehydes along with numerical simulations are used to illustrate importance of multicentred adsorption considerations in understanding selectivity behavior.