Wang Yonggen, Yin Zhibo, Zhu Yanpeng, Gu Jiajian, Li Yang, Wang Jiaobing
School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China.
Instrumental Analysis and Research Center, Sun Yat-Sen University, Guangzhou, 510275, China.
Angew Chem Int Ed Engl. 2019 Jan 8;58(2):587-591. doi: 10.1002/anie.201811706. Epub 2018 Dec 12.
Herein we present the first hexapole [9]helicene (H9H). Co-catalyzed [2+2+2] cyclotrimerization of a dinaphthopyrene (DNP) functionalized alkyne provides the hexaaryl benzene precursor 2, which is transformed into H9H via a dehydrocyclization reaction. Formation of each embedded [9]helicene involves forging of a new C-C bond, which stitches together two [4]helicene subunits of the neighboring DNP blades, reminiscent of the initial method Martin developed for the preparation of [9]helicene in the 1960s. Single-crystal X-ray analysis of both 2 and H9H discloses their extremely distorted and crowded structural features. Chiral resolution, optical and electronic properties of H9H are also presented.
在此，我们展示了首个六极[9]螺旋烯（H9H）。双萘并芘（DNP）官能化炔烃的共催化[2+2+2]环三聚反应提供了六芳基苯前体2，其通过脱氢环化反应转化为H9H。每个嵌入的[9]螺旋烯的形成都涉及形成一个新的C-C键，该键将相邻DNP叶片的两个[4]螺旋烯亚基连接在一起，这让人想起马丁在20世纪60年代开发的制备[9]螺旋烯的最初方法。对2和H9H进行的单晶X射线分析揭示了它们极其扭曲和拥挤的结构特征。还介绍了H9H的手性拆分、光学和电子性质。
