Self-Disproportionation of Enantiomers via Sublimation (SDEvS) Is an Emergent Property of Chiral Solids That Is Unaffected by Divergent Sample Histories

Self-disproportionation of enantiomers via sublimation (SDEvS) is widely observed, yet its mechanistic origin remains elusive. One unresolved question is whether the phenomenon is primarily governed by the intrinsic properties of chiral solids or by differences in sample preparation, which vary considerably across published studies. Here, we systematically compare six representative preparation protocols, including mechanical mixing, grinding, solvent-mediated recrystallization, and the preparation of different crystal compositions, using amides N-acetyl-1-phenylethylamine (1, Ac-PEA), ethyl 2-acetamido-3-phenylpropanoate (2, N-Ac-α-Phe-OEt) and tert-butyl N-(1-phenylethyl)carbamate (3) as model compounds. Despite measurable variations in the extent of enantiomeric enrichment, all preparation methods led to the same qualitative SDE behavior for the investigated systems. Sample preparation therefore acts only as a secondary factor, modulating the efficiency of enantiomeric fractionation without altering its overall direction. These findings demonstrate that sublimation-induced SDE is an emergent property of the chiral solid rather than an artifact of sample history. Our results provide a foundation for comparing data obtained under different experimental protocols and represent an important step toward a unified mechanistic understanding of sublimation-induced SDE.