Chiral Triphenylacetic Acid Esters: Residual Stereoisomerism and Solid-State Variability of Molecular Architectures,The Journal of Organic Chemistry

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Chiral Triphenylacetic Acid Esters: Residual Stereoisomerism and Solid-State Variability of Molecular Architectures
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2021-04-28 , DOI: 10.1021/acs.joc.1c00279
Natalia Prusinowska _{1,

2} , Agnieszka Czapik ₁ , Marcin Kwit _{1,

2}

Affiliation

We have proven the usability and versatility of chiral triphenylacetic acid esters, compounds of high structural diversity, as chirality-sensing stereodynamic probes and as molecular tectons in crystal engineering. The low energy barrier to stereoisomer interconversion has been exploited to sense the chirality of an alkyl substituent in the esters. The structural information are cascaded from the permanently chiral alcohol (inducer) to the stereodynamic chromophoric probe through cooperative interactions. The ECD spectra of triphenylacetic acid esters are highly sensitive to very small structural differences in the inducer core. The tendencies to maximize the C–H···O hydrogen bonds, van der Waals interactions, and London dispersion forces determine the way of packing molecules in the crystal lattice. The phenyl embraces of trityl groups allowed, to some extent, the control of molecular organization in the crystal. However, the spectrum of possible molecular arrangements is very broad and depends on the type of substituent, the optical purity of the sample, and the presence of a second trityl group in the proximity. Racemates crystallize as the solid solution of enantiomers, where the trityl group acts as a protecting group for the stereogenic center. Therefore, the absolute configuration of the inducer is irrelevant to the packing mode of molecules in the crystal.

中文翻译：

手性三苯乙酸酯：分子结构的残余立体异构性和固态可变性

我们已经证明了手性三苯乙酸酯、高结构多样性化合物、手性传感立体动力学探针和晶体工程中分子构造的可用性和多功能性。立体异构体互变的低能垒已被用来检测酯中烷基取代基的手性。结构信息通过协作相互作用从永久手性醇（诱导剂）级联到立体动力学发色探针。三苯乙酸酯的 ECD 光谱对诱导物核心中非常小的结构差异高度敏感。最大化C-H·O氢键的倾向、范德华相互作用和伦敦色散力决定了分子在晶格中的堆积方式。苯基包含三苯甲基，在某种程度上可以控制晶体中的分子组织。然而，可能的分子排列范围非常广泛，并且取决于取代基的类型、样品的光学纯度以及附近是否存在第二个三苯甲基。外消旋体作为对映体的固溶体结晶，其中三苯甲基充当立体中心的保护基团。因此，诱导剂的绝对构型与晶体中分子的堆积方式无关。

更新日期：2021-05-07

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