Organic synthesis by means of breaking aromaticity via reduction

2023 Fiscal Year Final Research Report

• Project/Area Number: 19H00895
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Medium-sized Section 33:Organic chemistry and related fields
• Research Institution: Kyoto University
• Principal Investigator: Yorimitsu Hideki 京都大学, 理学研究科, 教授 (00372566)
• Project Period (FY): 2019-04-01 – 2023-03-31
• Keywords: 芳香環メタモルフォシス / 還元 / ケミカルスペース / ヘテロール

Outline of Final Research Achievements

By utilizing metallic lithium, we have established 1) a method for inserting various atoms, including boron and silicon, into the carbon-nitrogen bond in the indole ring and 2) a simple and convenient method for the synthesis of substituted heteroles such as siloles and phospholes via the corresponding dilithium reagents that are reductively generated from thiophenes.
We have established a method to construct carbazole and seven-membered dibenzoazepine skeletons by the reactions of dibenzothiophene dioxide with alkanamine and N-benzylbenzaldehyde imine, respectively, under basic conditions. Furthermore, the synthesis of a series of heteroatom-containing helicenes by utilizing aromatic ring metamorphosis has been established, which have clarified the usefulness of aromatic ring metamorphosis.

Free Research Field

有機化学

Academic Significance and Societal Importance of the Research Achievements

頑丈で安定なヘテロ芳香環を還元的に破壊・開裂する新手法を開発し、芳香環の骨格そのものを改変する斬新な有機合成手法を数多く創出できた。これらの革新的手法に基づき、窒素、ケイ素、ホウ素、リンなどを環内鍵元素とする未知の機能を秘めた新規エキゾチックヘテロ芳香族分子群を続々と生み出した。化学・医農薬・エレクトロニクス産業にまで波及する新しい芳香族化学の基盤となる。