Kanagaraj Kuppusamy, Wang Rui, Zhao Ming-Kai, Ballester Pablo, Rebek Julius, Yu Yang
Center for Supramolecular Chemistry & Catalysis and Department of Chemistry, College of Science, Shanghai University, Shanghai 200444, China.
Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), 43007 Tarragona, Spain.
J Am Chem Soc. 2023 Mar 15;145(10):5816-5823. doi: 10.1021/jacs.2c12907. Epub 2023 Mar 1.
A series of straight-chain (C7-C13) alkyl--methyl aldoximes (R-C(H)═NOMe) were synthesized with various functional groups at the remote ends (alkenes, halogen, -COOH, and NH). Their isomers about the C═N bond showed ∼60-40% -ratio in organic solutions. Surprisingly, their confinement in a water-soluble capsule with benzoselenodiazole walls shows high selectivity for the -/-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 to -isomer selectivity (>99%) and was used in separation. The - isomerization occurred only in the capsular cavity at room temperature and was accelerated 10-fold by sonication. The -isomer selective binding, separation, and - isomerization are supported by NMR, DOSY, and computational studies.
合成了一系列直链（C7 - C13）烷基 - 甲基醛肟（R - C(H)═NOMe），其远端带有各种官能团（烯烃、卤素、-COOH和NH）。它们围绕C═N键的异构体在有机溶液中的比例约为60 - 40%。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时，对反式/顺式异构体表现出高选择性。它们在室温下对硫族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个重原子的链长度表现出特别高的反式到顺式异构体选择性（>99%），并用于分离。顺式异构化仅在室温下的胶囊腔内发生，超声处理可使其加速10倍。反式异构体的选择性结合、分离和顺式异构化得到了核磁共振（NMR）、扩散有序光谱（DOSY）和计算研究的支持。
