Development of catalytic enatioselective method for [2.2]-cyclophanes and its application as a novel chiral element

2019 Fiscal Year Final Research Report

• Project/Area Number: 16K05685
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Tokyo University of Agriculture and Technology
• Principal Investigator: Keiji Mori 東京農工大学, 工学(系)研究科(研究院), 准教授 (10515076)
• Project Period (FY): 2016-04-01 – 2020-03-31
• Keywords: [2.2]-パラシクロファン / 不斉触媒 / C-Nカップリング

Outline of Final Research Achievements

Although [2.2]-paracyclophane unit have been recognized as a potential chiral element, which can be used as a chiral ligand and organocatalysts, effective catalytic enantioselective synthetic method was scarce. We achieved the efficient catalytic method for the enantioselective synthesis of dihydroxy analogue of [2.2]-paracyclophane, namely, PHANOL by means of chiral phosphoric acid.
Unfortunately, both the applications of this asymmetric reaction to the PHANOL-analogue and some synthetic transformation were trouble some, and no desired results were obtained. Extensive screening of the reaction conditions offered unexpected results; 1,8-diaryl naphthalenes, which could be recognized as a structural analogue of paracyclophane, is a promising alternatives to paracyclophane. In addition, unprecedented weak-base-promoted and transition metal free C-N coupling reaction for the construction of pai-conjugated molecule was also discovered.

Free Research Field

有機合成化学、分子触媒化学

Academic Significance and Societal Importance of the Research Achievements

不斉反応において触媒の母核の担う役割は大きい。事実、新しい母核構造の登場が新しいキラル分子の製造に密接に関わってきた。本研究によりこれまで困難であった光学活性[2.2]-パラシクロファン類の入手が容易となるため、この構造を基盤とした新たな医薬・農薬開発へつながることが期待できる。
また、研究の途上で見出したC-Nカップリング法も有用である。π共役系分子は材料のみならず光触媒としても利用できる重要な化合物群である。本研究で見出した手法は従来法で多用される遷移金属を必要としないだけでなく、弱い塩基でも促進できるという利点も持つため、分解しやすい化合物の調製において有力な手法となりうる。