Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1 Kasuga-koen, Kasuga, 816-8580, Japan.
Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasuga-koen, Kasuga, 816-8580, Japan.
Chemistry. 2019 Nov 4;25(61):13855-13859. doi: 10.1002/chem.201903024. Epub 2019 Aug 28.
1,8,13-Trialkyl(aryl)silyl-9-hydroxytriptycenes (trisilyltriptycenes) were synthesized by the triple addition of ynolates and 3-silylbenzynes with high regioselectivity. Benzene rings in the resulting triptycenes were highly distorted where the dihedral angles between the substituents were as high as 35°. The distortion energy induced step-by-step halogenation reactions to yield halogenated triptycenes, including chiral triptycenes. The 1,8,13-trihalogenated triptycenes were then converted to 1,8,13-functionalized triptycenes.
1,8,13-三烷基（芳基）硅基-9-羟基苝（三硅基苝）通过炔醇盐和 3-硅基苯炔的三重加成反应以高区域选择性合成。所得三苝中的苯环高度扭曲，取代基之间的二面角高达 35°。这种扭曲能诱导逐步卤化反应，生成卤化三苝，包括手性三苝。然后，1,8,13-三卤化三苝被转化为 1,8,13-官能化三苝。
