Highly effective and selective synthesis of cyclic compounds utilizing reactivity of electron-deficient alkenes

2023 Fiscal Year Final Research Report

• Project/Area Number: 19K05476
• 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: Nara University of Education
• Principal Investigator: YAMAZAKI Shoko 奈良教育大学, 理科教育講座, 教授 (50182481)
• Project Period (FY): 2019-04-01 – 2024-03-31
• Keywords: 電子欠乏性アルケン / 分子内環化反応 / 環化付加 / Knoevenagel縮合 / ヘテロ環 / 炭素環 / スチレン / アルキン

Outline of Final Research Achievements

Highly effective and selective synthesis of cyclic compounds utilizing reactivity of electron-deficient alkenes has been achieved.
Inter- and intramolecular cycloaddition of ethenetricarboxylates with styrenes in the presence of Lewis acid gave cyclobutanes, stereoselectively. The intramolecular reactions of styrene-functionalized ethenetricaroxylate amides showed high diversity of reaction modes. Heating α-bromostyrene-functionalized amides of monomethyl fumarate with Et3N gave 1,4-dihydronaphthalenes. Dehydrogenation of various 1,4-dihydronaphthalenes gave naphthalene derivatives. Intramolecular cyclization reactions of arylpropargyl amides of electron-deficient α,β-alkenyl carboxylates gave benz[f]isoindolines and aroyl pyrrolidines depending on the reaction conditions. Sequential Knoevenagel condensation/cyclization leading to indenes and benzofulvenes have also been developed. The reaction mechanisms have been studied using DFT calculations.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

高温、低温を必要としない、ワンポット多結合形成による、低エネルギー型、短工程の環化合物骨格の選択的な新合成反応開発を達成した。環境負荷軽減に貢献することができる。
種々の置換基を用いて電子的、立体的効果による反応性、選択性の違いを調べ、計算化学を用いて、起こりうる反応経路を詳細に調べることにより、反応が成功する鍵となる因子、選択性を解明した。蛍光などの物性を持つ多修飾環化合物の合成も達成した。含窒素、酸素などのヘテロ環、炭素環をもつ生物活性のある物質や、機能性有機材料開発が期待される。