Mechanistic Studies and Development of Catalytic Palladium Enolate Umpolung Reactions

2021 Fiscal Year Final Research Report

• Project/Area Number: 18K05105
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Kagawa National College of Technology (2019-2021); Osaka University (2018)
• Principal Investigator: Takenaka Kazuhiro 香川高等専門学校, 一般教育科(詫間キャンパス), 講師 (20423113)
• Project Period (FY): 2018-04-01 – 2022-03-31
• Keywords: パラジウム触媒 / エノラート / 極性転換 / カルボニル化合物

Outline of Final Research Achievements

Palladium enolates, which commonly act as nucleophiles, are known to react with an electrophile. We have succeeded in the development of new catalytic reactions involving nucleophilic interception of the palladium enolate. This umpolung process furnishes an efficient route to densely functionalized carbonyl compounds by way of ring-closing carbon-carbon bond formation and subsequent nucleophilic attack at the resulting palladium enolate intermediate. It is also revealed that fine-tuning of the electron density on the palladium complex is crucial for this enolate umpolung process.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

アミノ酸のようなカルボニル基のα位に官能基をもつ化合物は、医薬品や農薬など様々な製品に利用され、現代生活の基盤を支える重要な物質である。本研究では常識にとらわれず、一般的に知られた反応性を逆転させることで新しい反応を実現した。見出した成果は、画期的な合成戦略の提案、生産コストの削減や新規化合物の設計といったカルボニル化合物の製造に多大な影響をもたらすと期待できる。