catalytic synthesis of saddle-shaped pi-conjugated molecules by aromatic ring construction and their fundamental properties

2022 Fiscal Year Final Research Report

• Project/Area Number: 21K18949
• 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: Tokyo Institute of Technology
• Principal Investigator: Tanaka Ken 東京工業大学, 物質理工学院, 教授 (40359683)
• Project Period (FY): 2021-07-09 – 2023-03-31
• Keywords: 有機合成化学 / 不斉合成化学 / 構造有機化学

Outline of Final Research Achievements

Non-planar graphene has a group of molecules with non-central chirality derived from its 3D structure. Their asymmetric synthesis has been a challenging target in organic synthesis because of two difficulties: overcoming high steric hindrance/stereo-distortion and constructing non-central chirality. In this research, we designed a new substrate design combining linear and horseshoe-shaped aromatic ring parts and a synthetic method that "twists the molecular belt" while "suppressing strain energy" was devised. By using the asymmetric rhodium-catalyzed reaction developed by the research group for this new synthetic method, they achieved the catalytic asymmetric synthesis of aromatic ring belts with a twist of up to 540 degrees, including giant saddle-shaped molecules.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

本研究成果の巨大な鞍型分子を含む複雑なトポロジーをもつ芳香族化合物は、従来の有機分子にはない特異な光学特性や電子特性を示す可能性を秘めており、広範な機能性有機材料の創製に貢献できると期待される。また、本研究では不斉ロジウム触媒を用いることで分子のねじれ方向が制御できることを示した。これは未開拓なツイストキラリティの化学を切り開く成果であり、円偏光発光材料や3次元ディスプレイといったキラル光学材料への応用が期待され、社会的波及効果も大きい。