The demand for enantiopure chemicals, for example, natural products, pharmaceuticals, or materials, has been increasing rapidly for years, and the global market is continually expanding.[1] In the field of asymmetric catalysis, transitionmetal catalysts using chiral ligands represent one of the most effective and versatile approaches.[2] However, the development of highly efficient catalysts is often an unpredictable, challenging, and time-consuming process. Accordingly, every method that shortens this laborious procedure or allows an assessment of selectivity contributions is highly valued. In this context, rational models were developed to predict asymmetry in resulting products, for example, Crams rule and the Felkin-Anh model, [3] and quadrant models. [4,5] Furthermore, combinatorial libraries provide empirical strategies for ligand selection. [6][7][8] With regard to temperature optimization, the isoinversion principle provides a general model for reactions with two or more selectivity steps.[9] At present, the rational models have to address more complex issues because of the importance of noncovalent interligand interactions in organometallic complexes.[10] Even weak p-p interactions were found to influence complex structures, [11,12] for example, a cis coordination of the ligands was found for a bis(phosphonite) Pt complex and a bis(phosphoramidite) Pd complex; this coordination was explained by weak intermolecular interactions. [13,14] In a recent study, we reported a temperature-dependent interconversion, which was potentially caused by interligand interactions, of various phosphoramidite copper complexes. [15] This result raised the question of whether there is a fast and easy way to predict ligand-driven changes of the active catalysts, either by interconversion or by aggregation phenomena. However, to the best of our knowledge, no simple and general procedure has been presented to date that reliably predicts temperature-dependent changes of transition-metal catalyst sizes. Such a prediction would allow a fast determination of the temperature range applicable to the desired catalytic reaction.Herein, we present the first aggregation study of selected phosphoramidite ligands and their transition-metal complexes. The aggregation trends of the ligands, the complexes of which can catalyze highly enantioselective reactions, reveal that an easy and fast DOSY screening of the free ligands allows a prediction of the aggregation trends of their transition-metal complexes, even without knowledge about their structures. In addition, the applicability limits of this method are discussed and the type of interligand interactions is addressed.Chiral phosphoramidites have emerged as one of the privileged ligand structures, with increasing applications in various asymmetric catalytic reactions with excellent enantioselectivies. [16][17][18][19][20][21][22][23] Therefore, 1 and 2 (Scheme 1), which show high selectivities in catalysis, were chosen as model systems that represent the well-known binaphthol-and biphenolbas...