Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Angew Chem Int Ed Engl. 2017 Jun 12;56(25):7151-7155. doi: 10.1002/anie.201703008. Epub 2017 May 15.
Corona[5]arenes, a novel type of macrocyclic compound that is composed of alternating heteroatoms and para-arylenes, were synthesized efficiently by two distinct methods. In a macrocycle-to-macrocycle transformation approach, S -corona[3]arene[3]tetrazine underwent sequential S Ar reactions with HS-C H -X-C H -SH (X=S, CH , CMe , SO , and O) to produce the corresponding corona[3]arene[2]tetrazines. Different corona[3]arene[2]tetrazine compounds were also constructed in a straightforward manner by a one-pot three-component reaction of HS-C H -X-C H -SH (X=S, CH , CMe , SO , and O) with diethyl 2,5-dimercaptoterephthalate and 2 equiv of 3,6-dichlorotetrazine under very mild conditions. All corona[5]arenes adopted 1,2,4-alternate conformational structures in the crystalline state yielding similar nearly regular pentagonal cavities. Both the cavity size and the electronic property of the acquired macrocycles were fine-tuned by the nature of the bridging element X.
冠芳烃是一类新型的大环化合物，由交替的杂原子和para-芳基组成，我们通过两种截然不同的方法高效合成了冠芳烃。在大环套大环的转化方法中，S-冠[3]芳烃[3]四嗪依次与 HS-C H -X-C H -SH（X=S、CH 、CMe 、SO 、和 O）进行 S Ar 反应，生成相应的冠[3]芳烃[2]四嗪。HS-C H -X-C H -SH（X=S、CH 、CMe 、SO 、和 O）与二乙基 2,5-二巯基对苯二甲酸酯和 3,6-二氯四嗪的 2 当量在非常温和的条件下进行一锅三组分反应，也可以以直接的方式构建不同的冠[3]芳烃[2]四嗪化合物。所有冠[5]芳烃在晶体状态下都采用 1,2,4-交替构象，生成类似的几乎规则的五角形空腔。所得大环的空腔大小和电子性质都可以通过桥接元素 X 的性质进行精细调节。
