Synthesis of organic molecules based on tetrasubstituted triptycenes

2020 Fiscal Year Final Research Report

• Project/Area Number: 18H02557
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 47010:Pharmaceutical chemistry and drug development sciences-related
• Research Institution: Kyushu University
• Principal Investigator: Shindo Mitsuru 九州大学, 先導物質化学研究所, 教授 (40226345)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Keywords: トリプチセン / ベンザイン / かご分子 / 大環状化合物 / 環化付加

Outline of Final Research Achievements

Triptycene is a sterically rigid, highly symmetrical propeller-shaped organic compound. We aimed that, using triptycene as a foundation, three dimensional functional organic compounds are precisely synthesized by construction of stems perpendicularly upon the molecule. We have recently developed triple cycloaddition of an ynolate with arynes to afford triptycene in one-pot. Herein, we found selective synthesis of sterically congested 1,8,13-trisilyltriptycenes via the triple cycloaddition. Since this triptycene is highly distorted, the trisilyltriptycene was easily converted into 1,8,13-tribromotriptycene, which was then subjected to several metal-catalyzed coupling reactions to provide 1,8,13-trisubstituted U-shaped “cup” molecules. Starting from the cup molecules, a caged compound, sandwiched between triptycenes, was synthesized in good yield. Furthermore, the fixed units on the triptycene were connected to furnish macrocycles. Thus, triptycene-based syntheses were demonstrated.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

今回開発したトリプチセンの新規合成法は置換基の導入が可能な点で有意義である。特に1，8，13位に置換基を導入することができる初の合成法である。さらに、トリプチセンの構造的特徴を生かして、これを土台として、その平面から垂直に支柱ユニットを構築し、精密有機合成に活用するというテンプレート合成の新コンセプトを提示した。それに基づき、かご型のカプセル分子や、大環状化合物の効率的合成を達成した。この方法論では3次元空間の定まった座標に適切な官能基を配置できる特徴がある。大環状化合物は医薬品や分子包接さらにはカーボンナノチューブの原料として有用である。さらに人工酵素の開発などに応用できる。