通过多个氢键在π堆积大环中捕获酯水合物中间体。

Trapping an Ester Hydrate Intermediate in a π-Stacked Macrocycle with Multiple Hydrogen Bonds.

作者信息

Wang Bin, Nan Zi-Ang, Li Qing, Liu Jin, Lu Zi-Xiu, Wang Wei, Zhuo Zhu, Li Guo-Ling, Huang You-Gui

机构信息

CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China.

Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108, China.

出版信息

Molecules. 2023 Jul 28;28(15):5705. doi: 10.3390/molecules28155705.

DOI:10.3390/molecules28155705

PMID:37570674

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10420806/

Abstract

Ester hydrates, as the intermediates of the esterification between acid and alcohol, are very short-lived and challenging to be trapped. Therefore, the crystal structures of ester hydrates have rarely been characterized. Herein, we present that the mono-deprotonated ester hydrates [CHOSO(OH)], serving as the template for the self-assembly of a π-stacked boat-shaped macrocycle (CHOSO(OH))(CHOSO)@{[ClLCo]}·Cl·13CHOH·9HO () (L = tris(2-benzimidazolylmethyl) amine), can be trapped in the host by multiple NH···O hydrogen bonds. In the solution of CoCl, L, and HSO in MeOH, HSO reacts with MeOH, producing [CHOSO] via the ester hydrate intermediate of [CHOSO(OH)]. Both the product and the intermediate serve as the template directing the self-assembly of the π-stacked macrocycle, in which the short-lived ester hydrate is firmly trapped and stabilized, as revealed by single-crystal analysis.

摘要

酯水合物作为酸与醇酯化反应的中间体，寿命极短，难以捕获。因此，酯水合物的晶体结构很少被表征。在此，我们展示了单去质子化的酯水合物[CHOSO(OH)]，作为π-堆积船形大环(CHOSO(OH))(CHOSO)@{[ClLCo]}·Cl·13CHOH·9HO ()（L = 三(2-苯并咪唑基甲基)胺）自组装的模板，可通过多个NH···O氢键被困在主体中。在CoCl、L和HSO于甲醇中的溶液中，HSO与甲醇反应，通过[CHOSO(OH)]的酯水合物中间体生成[CHOSO]。产物和中间体均作为模板指导π-堆积大环的自组装，单晶分析表明，寿命短暂的酯水合物在其中被牢固捕获并稳定下来。