Uchida Yoshiaki, Iwama Sekai, Coquerel Gérard, Tamura Rui
Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 606-8502, Japan.
PRESTO (Japan) Science and Technology Agency, Kawaguchi, Saitama, 332-0012, Japan.
Chemistry. 2016 Aug 8;22(33):11660-6. doi: 10.1002/chem.201601550. Epub 2016 Jul 13.
The kinetic/thermodynamic origin of preferential enrichment (PE), which is a spontaneous enantiomeric resolution phenomenon applicable to racemic crystals, is described. The mechanism of PE, which was unveiled with respect to the first-generation of chiral organic compounds showing PE, has been interpreted in terms of a nonlinear complexity phenomenon including two unique processes: a solvent-assisted solid-to-solid polymorphic transition and subsequent selective redissolution of the excess one enantiomer from the transformed disordered crystals into the mother liquor. The present works confirm that PE takes place because of the unique nonlinear solubility properties of the two enantiomers after the occurrence of a polymorphic transition under PE crystallization conditions at high supersaturation. Furthermore, a ternary phase diagram that is consistent with the mechanism of PE is proposed.
描述了优先富集（PE）的动力学/热力学起源，这是一种适用于外消旋晶体的自发对映体拆分现象。关于第一代表现出PE的手性有机化合物所揭示的PE机制，已根据非线性复杂性现象进行了解释，该现象包括两个独特过程：溶剂辅助的固-固多晶型转变以及随后过量的一种对映体从转变后的无序晶体中选择性再溶解到母液中。目前的研究证实，在高过饱和度的PE结晶条件下发生多晶型转变后，由于两种对映体独特的非线性溶解特性，PE得以发生。此外，还提出了与PE机制一致的三元相图。
