Selective Binding and Isomerization of Oximes in a Self-Assembled Capsule,Journal of the American Chemical Society

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Selective Binding and Isomerization of Oximes in a Self-Assembled Capsule
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-03-01 , DOI: 10.1021/jacs.2c12907
Kuppusamy Kanagaraj ₁ , Rui Wang ₁ , Ming-Kai Zhao ₁ , Pablo Ballester _{2,

3} , Julius Rebek _{1,

4} , Yang Yu ₁

Affiliation

A series of straight-chain (C7–C13) alkyl-O-methyl aldoximes (R–C(H)═NOMe) were synthesized with various functional groups at the remote ends (alkenes, halogen, −COOH, and NH₂). Their isomers about the C═N bond showed ∼60–40% E–Z-ratio in organic solutions. Surprisingly, their confinement in a water-soluble capsule with benzoselenodiazole walls shows high selectivity for the cis-/Z-isomer. Their relative affinities for the chalcogen-bonded capsule at room temperature depend mainly on the guest chain length and functional groups. A chain length of 14 heavy atoms showed especially high E- to Z-isomer selectivity (>99%) and was used in separation. The E–Z isomerization occurred only in the capsular cavity at room temperature and was accelerated 10-fold by sonication. The Z-isomer selective binding, separation, and E–Z isomerization are supported by NMR, DOSY, and computational studies.

中文翻译：

自组装胶囊中肟的选择性结合和异构化

合成了一系列在远端具有各种官能团（烯烃、卤素、-COOH 和 NH _{2 ）的直链 (C7–C13) 烷基}-O-甲基醛肟 (R–C(H)=NOMe )。它们关于 C=N 键的异构体在有机溶液中显示出 ~60–40% E - Z-比率。令人惊讶的是，将它们限制在具有苯并硒二唑壁的水溶性胶囊中显示出对顺式- / Z - 异构体的高选择性。它们在室温下对硫属元素键合胶囊的相对亲和力主要取决于客体链长度和官能团。14 个重原子的链长显示出特别高的E-到Z-异构体选择性 (>99%) 并用于分离。E - Z异构化仅在室温下发生在囊腔中，并通过超声加速 10 倍。NMR、DOSY 和计算研究支持Z异构体选择性结合、分离和E - Z异构化。

更新日期：2023-03-01

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