Institute for Materials Chemistry and Engineering, Kyushu University, 6-1, Kasugako-en, Kasuga, 816-8580, Japan.
Interdisciplinary Graduate School of Engineering Science, Kyushu University, 6-1, Kasugako-en, Kasuga, 816-8580, Japan.
Chemistry. 2023 Jul 11;29(39):e202300988. doi: 10.1002/chem.202300988. Epub 2023 May 16.
Herein, we describe Hiyama coupling via intramolecular substituent transfer from silicon on one blade of triptycenes to another to yield 1,8,13-trisubstituted chiral triptycenes. This reaction is attributed to the proximity effect of substituents on triptycene, which plays an important role in not only the formation of the oxy-palladacycle but also the activation of the silyl group to facilitate σ-bond metathesis. After bromination and nucleophilic ring opening, the second intramolecular Hiyama coupling provided various 1,8,13-trisubstituted chiral triptycenes. The optical resolution of 1,8,13-triptycene afforded an optically active form for the first time.
在此，我们描述了通过希亚马（Hiyama）偶联反应，在三叶芴的一个支链上的硅原子通过分子内取代基转移到另一个支链上，生成 1,8,13-三取代的手性三叶芴。该反应归因于三叶芴上取代基的临近效应，它在手性三叶芴的氧钯环形成以及硅基活化以促进 σ-键复分解反应中都起着重要作用。溴化和亲核开环后，第二次分子内希亚马偶联反应提供了各种 1,8,13-三取代的手性三叶芴。1,8,13-三叶芴的光学拆分首次得到了光学活性形式。
