Guo Qing-Hui, Zhao Liang, Wang Mei-Xiang
Key Laboratory of Bioorganic Phosphorous Chemistry and Chemical Biology, Department of Chemistry, Tsinghua University, Beijing, 100084, P. R. China.
Chemistry. 2016 May 10;22(20):6947-55. doi: 10.1002/chem.201600462. Epub 2016 Apr 8.
We report herein the synthesis, structure, and molecular recognition of S6 - and (SO2 )6 -corona6arenes, and demonstrate a unique and efficient strategy of regulating macrocyclic conformation and properties by adjusting the oxidation state of the heteroatom linkages. The one-pot nucleophilic aromatic substitution reaction of 1,4-benzenedithiol derivatives, biphenyl-4,4'-dithiol and 9,9-dipropyl-9H-fluorene-2,7-dithiol with 3,6-dichlorotetrazine afforded S6 -corona[3]arene[3]tetrazines. These compounds underwent inverse-electron-demand Diels-Alder reaction with enamines and norbornadiene to produce S6 -corona[3]arene[3]pyridazines. Facile oxidation of sulfide linkages yielded (SO2 )6 -corona[3]arene[3]pyridazines. All corona6arenes adopted generally hexagonal macrocyclic ring structures; however, their electronic properties and conformation could be fine-tuned by altering the oxidation state of the sulfur linkages. Whereas (SO2 )6 -corona[3]arene[3]pyridazines were electron-deficient, S6 -corona[3]arene[3]pyridazines acted as electron-rich macrocyclic hosts that recognized various organic cations in both aqueous and organic solutions.
我们在此报告S6 -和(SO2 )6 -冠6芳烃的合成、结构及分子识别，并展示了一种通过调节杂原子连接键的氧化态来调控大环构象和性质的独特且高效的策略。1,4 -苯二硫醇衍生物、联苯 - 4,4'-二硫醇和9,9 -二丙基 - 9H -芴 - 2,7 -二硫醇与3,6 -二氯四嗪的一锅法亲核芳香取代反应制得S6 -冠[3]芳烃[3]四嗪。这些化合物与烯胺和降冰片二烯发生逆电子需求的狄尔斯 - 阿尔德反应，生成S6 -冠[3]芳烃[3]哒嗪。硫化物连接键的简易氧化得到(SO2 )6 -冠[3]芳烃[3]哒嗪。所有冠6芳烃通常都采用六边形大环结构；然而，它们的电子性质和构象可通过改变硫连接键的氧化态进行微调。(SO2 )6 -冠[3]芳烃[3]哒嗪是缺电子的，而S6 -冠[3]芳烃[3]哒嗪作为富电子的大环主体，在水相和有机相中都能识别各种有机阳离子。
