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2016 年度 実施状況報告書

Dual Catalysis with Photoredox Catalysts for Organic Transformations Mediated by Single-Electron Transfer Processes

研究課題

研究課題/領域番号 16K17865
研究機関東京大学

研究代表者

ユー ウージン  東京大学, 大学院理学系研究科(理学部), 特任助教 (70626077)

研究期間 (年度) 2016-04-01 – 2018-03-31
キーワードcarbon dioxide / C-H functionalization / copper / silicon
研究実績の概要

The proposed research was based on the concept of activation of organo- and transition metal catalysts by single-electron transfers (SET) mediated by light-induced photoredox catalysts. However, during the research period, the popularity of coupling photoredox catalysts with other catalytic systems grown significantly, and we felt that we could not compete with other large international research groups. As such, we decided to focus on developing new synthetic methods utilizing carbon dioxide.

In that vein, we have focused on utilizing carbon dioxide as a sustainable source of a carbon feedstock to prepare various organic molecules of biological interests. Since carbon dioxide is such a simple building block, our overall research goal was to develop multi-component coupling/step reactions with carbon dioxide. In light of the importance of phthalides in medicinal and agricultural sciences, we developed a new protocol that combined carbon-hydrogen bond activation with a carboxylation process to convert benzyl alcohols to phthalides. We found that a wide range of functional groups was tolerated under our reaction conditions, and that we could apply our methodology for the preparation of various natural products.

現在までの達成度 (区分)
現在までの達成度 (区分)

2: おおむね順調に進展している

理由

The funded research was based on the desire to utilize visible light as an alternative energy source to mediate chemical reactions, and that we did not focus on this topic based on the current international research trend. As such, there was no progress for the funded research.

On the other hand, we have redirected the resources provided by the research grant monies to develop new carboxylation reactions. The conversion of carbon dioxide, a greenhouse gas, into useful organic compounds is an important goal from both an academic and industrial prospective, and we found made significant progress in this field. As such, we can state the research progress in developing organic transformations with carbon dioxide has advanced quite well, and we anticipate further developments in this field.

今後の研究の推進方策

We plan to investigate further the use of carbon dioxide as a building block in organic synthesis by developing new synthetic methods and catalysts. Based on our previous work in synthesizing phthalides (5-membered lactones), we wish to expand upon this chemistry further to prepare a wide array of lactones using the approach of C-H activation and carboxylation chemistry. To achieve this, we will need to develop new catalysts that will enable the C-H activation of a wide variety of alcohols, and find new catalysts that will facilitate the carboxylation reaction of the reaction intermediates.

We will also investigate other kinds of multi-component coupling reactions that incorporate carbon dioxide. We have some preliminary data that suggest that we can synthesize trifluoromethylated carboxylic acids via fluorocarboxylation of 1,1-difluoroalkenes, and we are working towards the completion of this project.

  • 研究成果

    (3件)

すべて 2017 2016

すべて 雑誌論文 (1件) (うち国際共著 1件、 査読あり 1件) 学会発表 (2件) (うち国際学会 1件)

  • [雑誌論文] Incorporation of Carbon Dioxide into Phthalides via Ligand-Free Copper-Catalyzed Direct Carboxylation of Benzoxasiloles2017

    • 著者名/発表者名
      Thanh V. Q. Nguyen, Jose A. Rodriguez-Santamaria, Woo-Jin Yoo, Shu Kobayashi
    • 雑誌名

      Green Chemistry

      巻: 19 ページ: 2501-2505

    • DOI

      10.1039/C7GC00917H

    • 査読あり / 国際共著
  • [学会発表] Ligand-Free Copper Catalyzed Direct Carboxylation of Arylsilanes with Carbon Dioxide2017

    • 著者名/発表者名
      Thanh V. Q. Nguyen, Woo-Jin Yoo, Shu Kobayashi
    • 学会等名
      The 87th Chemical Society of Japan Annual Meeting
    • 発表場所
      Hiyoshi Campus, Keio University, Kanagawa, Japan
    • 年月日
      2017-03-16 – 2017-03-19
  • [学会発表] Synthesis of Phthalides via Copper-Catalyzed Direct Carboxylation of Benzoxasiloles2016

    • 著者名/発表者名
      Woo-Jin Yoo, Thanh V. Q. Nguyen, Jose A. Rodriguez-Santamaria, and Shu Kobayashi
    • 学会等名
      21st International Conference on Organic Synthesis
    • 発表場所
      Bombay, Mumbai, India
    • 年月日
      2016-12-11 – 2016-12-16
    • 国際学会

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公開日: 2018-01-16  

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