Synthesis of semi-rigid organic cage compounds sandwiched between iptycenes

2022 Fiscal Year Final Research Report

• Project/Area Number: 20K21198
• Research Category: Grant-in-Aid for Challenging Research (Exploratory)
• Allocation Type: Multi-year Fund
• Review Section: Medium-sized Section 33:Organic chemistry and related fields
• 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): 2020-07-30 – 2023-03-31
• Keywords: トリプチセン / ベンザイン / かご分子 / イノラート

Outline of Final Research Achievements

We have already found a novel method for the synthesis of 1,8,13-substituted trisilyltriptycenes via three consecutive cycloaddition reactions of ynolates with silylbenzynes. Using this method, we aimed to synthesize covalent semi-rigid nonmetallic organic cage compounds consisting of two molecules of iptycenes as a bottom and a cap connected by multiple pillars. Trisilyltriptycene was converted to tribromotriptycene, on which the pillars were formed by metal-catalyzed coupling reaction. The cage compounds were synthesized in high yield by condensation of the bottom triptycene with triformyltriptycene. Similarly, a vase-shaped cage compounds were also synthesized. We also found the synthesis of chiral triptycenes by sequential reactions in which palladium catalyzes four reactions, and the ring-opening reactions of triptycenes.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

トリプチセンという剛直なプロペラ型分子を底と蓋とするような半剛直カゴ分子の合成に成功した。将来、トリプチセンをイプチセンに拡張することで「底」と「蓋」の大きさを拡大し、さらに支柱の本数、長さ、幅を調整することによりカゴ分子の内孔の大きさを自在に調整することができると考えられる。このかご分子は、その内部の分子空間を利用した高度な分子認識や触媒機能の発現、また、規則的な配列をもつ細孔材料等に展開可能と考える。以上、本成果は、ホストゲスト化学、酸塩基複合触媒機能、多孔性材料、ドラッグデリバリーシステム、不安定分子の隔離安定化などに応用可能なカゴ分子の合成法を提供するものである。