Construction of Hydrogen‐Bonded Ternary Organic Crystals Derived from L‐Tartaric Acid and Their Application to Enantioseparation of Secondary Alcohols

Abstract

Ternary organic crystals consisting of an L-tartaric acid-derived dicarboxylic acid, a commercially available achiral diamine, and a chiral secondary alcohol have been developed and characterized by X-ray crystallography. 1D, 2D, and 3D hydrogen-bonded supramolecular networks were constructed, depending on the structure of the diamine used. Benzylic and aliphatic secondary alcohols were enantioselectively incorporated into the crystal and were successfully enantioseparated with up to 86 and 79% enantiomeric excess (ee), respectively. Selective incorporation of one enantiomer of 2-butanol, which is a small chiral aliphatic alcohol, was achieved by the cooperative effects of hydrogen bonds, CH···π interactions, and van der Waals interactions between the guest and host molecules, with the aid of two water molecules. The high host potential of the binary supramolecular system is mainly attributed to the skewed conformation of two rigid aromatic groups of tartaric acid derivatives, which prevents dense packing of the molecules and enhances the formation of multicomponent inclusion crystals.

Negative nonlinear CD-<italic>ee</italic> dependence in dibenzoyltartaric acid induced aggregates of perylenebisimide

“…由苝酰亚胺衍生物吸收光谱计算所得的A 0-0 /A 0-1 可资聚集度计算, 是衡量苝分子耦合数量的重要参 数 [11] . 对二苯甲酰酒石酸中内消旋体摩尔分数不同的 PBIEtGua/DboTar聚集体进行变温吸收光谱实验, 得 Hirose等 [19] 曾报道手性二苯甲酰酒石酸以New-man投影式结构存在于溶液中(图S12). Shinkai等 [20] Abstract: Supramolecular chirality of aggregates can be described in terms of the CD signals of the aggregates as a function of the enantiomeric excess of the chiral building block or chiral inducer.…”

Synthesis and Experimental Studies on Supramolecular Synthons of Aminoguanidinium Carboxylates: A Case Study of π‐HoleBonded Carbon Bonding via Theoretical Approaches

“…Organic salts are of great interest among the multicomponent crystals (e. g., co‐crystals, hydrates, and solvates) and their synthesis remains active topic in the field of crystal engineering. Basically salt units are resulting from the tunable acid‐base chemistry involved between the complimentary organic components . The unique advantages of these ion–pair assemblies are high polarity, superior thermal stability and flexible crystal packing, which play a vital role in improving the physicochemical properties (solubility, melting point, dissolution rate) of active pharmaceutical ingredients (APIs) .…”

Crystal structure and hydrogen bonding in the hydrated cocrystalline salt tryptaminium–3,5-dinitrobenzoate–quinoline–water (3/3/2/2)

“…In many cases, the addition of solvent molecules and/or water molecules increased the number of component molecules in the lattice. Throughout this time, consideration has also been given to ternary systems and examples of their preparation and their applications in crystal engineering have been described (Kodami et al, 2011;Adsmond et al, 2016;Topić & Rissanen, 2016). Current definitions of a tertiary system indicate that solvent molecules are excluded from the molecule count of the system (Sharma et al, 1993).…”