Development of Method for Molecular Transformations Based on Photoredox Reaction of Quinones

• Project/Area Number: 26810018
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: ANDO Yoshio 東京工業大学, 理学院, 助教 (40532742)
• Project Period (FY): 2014-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2016: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2015: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2014: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: 有機合成化学 / キノン / 光化学反応 / 天然物 / 全合成 / ナフトキノン / CH官能基化 / 酸化還元 / 立体特異的合成

Outline of Final Research Achievements

Quinones are widely distributed in nature as pigments and bioactive molecules. Some quinones show particular reactivity under photo-irradiation. However, such reactivity has been overlooked and not been employed in organic synthesis so far.
In this research, a new synthetic method for organic compounds, which have been unachievable by conventional method, was developed by exploiting photoredox reaction of quinones. The substrate scope has been clarified. Moreover, it was found that the photoredox reaction proceeds with stereospecific manner. As the application, the first enantioselective total synthesis of spiroxin C, dimerized naphthoquinone natural product, has been accomplished by employing stereospecific photoredox reaction as the key step.

Research Products

• [Journal Article] Intramolecular Photoredox Reaction of Naphthoquinone Derivatives (2017)
  • Author(s): Yoshio Ando, Takashi Matsumoto, Keisuke Suzuki
  • Journal Title: Synlett Volume: 28 Issue: 09 Pages: 1040-1045
  • DOI: 10.1055/s-0036-1589001
  • Peer Reviewed
• [Journal Article] Stereospecificity in Intramolecular Photoredox Reactions of Naphthoquinones: Enantioselective Total Synthesis of (－)-Spiroxin C (2017)
  • Author(s): Yoshio Ando, Atsuko Hanaki, Ryota Sasaki, Ken Ohmori, Keisuke Suzuki
  • Journal Title: Angewandte Chemie International Edition Volume: 56 Issue: 38 Pages: 11460-11465
  • DOI: 10.1002/anie.201705562
  • Peer Reviewed
• [Presentation] 連続的酸化還元反応を鍵とするスピロキシンAの全合成研究 (2018)
  • Author(s): 安藤吉勇、佐々木亮太、大森建、鈴木啓介
  • Organizer: 日本化学会第９８春季年会
• [Presentation] スピロキシンAの合成研究：合成中間体の保護基の検討 (2018)
  • Author(s): 田中大裕、佐々木亮太、安藤吉勇、大森建、鈴木啓介
  • Organizer: 日本化学会第９８春季年会
• [Presentation] 分子内光酸化還元反応を鍵とするγ-ルブロマイシンの全合成研究 (2017)
  • Author(s): 脇田 文博、安藤 吉勇、大森 建、鈴木 啓介
  • Organizer: 日本化学会第９７春季年会
  • Place of Presentation: 慶應義塾大学日吉キャンパス （横浜）
  • Year and Date: 2017-03-18
• [Presentation] Total synthesis of γ-rubromycin by exploiting intramolecular photoredox reaction (2017)
  • Author(s): Fumihiro Wakita, Yoshio Ando, Ken Ohmori, Keisuke Suzuki
  • Organizer: 10th Workshop on Organic Chemistry for Junior Chemist (WOCJC-10)
  • Place of Presentation: National Tsing Ua University （Hsinchu, Taiwan
  • Year and Date: 2017-01-06
  • Int'l Joint Research
• [Presentation] Stereospecificity in Intramolecular Photoredox Reactions of Naphthoquinones: Enantioselective Total Synthesis of (-)-Spiroxin C (2017)
  • Author(s): Yoshio Ando, Atsuko Hanaki, Ryota Sasaki, Takashi Matsumoto, Ken Ohmori, Keisuke Suzuki
  • Organizer: The 26th International Society of Heterocyclic Chemistry (26th ISHC Congress)
  • Int'l Joint Research
• [Presentation] Redox Reaction of Naphthoquinones: Total Syntheses of Spiroxin C and Engelharquinone (2016)
  • Author(s): Yoshio Ando
  • Organizer: ACP Lecureship Tour in China
  • Place of Presentation: Shaanxi Normal University, (Xi’an, China)
  • Year and Date: 2016-11-10
  • Int'l Joint Research / Invited
• [Presentation] Redox Reaction of Naphthoquinones: Total Syntheses of Spiroxin C and Engelharquinone (2016)
  • Author(s): Yoshio Ando
  • Organizer: ACP Lecureship Tour in China
  • Place of Presentation: Lanzhou University, (Lanzhou, China)
  • Year and Date: 2016-11-08
  • Int'l Joint Research / Invited
• [Presentation] 1,2-ナフトキノン誘導体を用いた分子内光酸化還元反応の開発研究 (2016)
  • Author(s): 脇田 文博、安藤 吉勇、大森 建、鈴木 啓介
  • Organizer: 第１０９回有機合成シンポジウム
  • Place of Presentation: 東京工業大学大岡山キャンパス （東京）
  • Year and Date: 2016-06-08
• [Presentation] ナフトキノンの特異な反応性を活用した天然物合成 (2016)
  • Author(s): 安藤 吉勇
  • Organizer: 第４回慶應有機化学若手シンポジウム
  • Place of Presentation: 慶應義塾大学矢上キャンパス （横浜）
  • Year and Date: 2016-05-07
  • Invited
• [Presentation] 1,2-ナフトキノン誘導体の分子内酸化還元反応 (2016)
  • Author(s): 脇田文博、安藤吉勇、大森建、鈴木啓介
  • Organizer: 日本化学会第９６春季年会
  • Place of Presentation: 同志社大学京田辺キャンパス (京都府)
  • Year and Date: 2016-03-26
• [Presentation] スピロキシンＡの全合成研究 (2016)
  • Author(s): 佐々木亮太、安藤吉勇、大森建、鈴木啓介
  • Organizer: 日本化学会第９６春季年会
  • Place of Presentation: 同志社大学京田辺キャンパス (京都府)
  • Year and Date: 2016-03-25
• [Presentation] ナフトキノン類の酸化還元能を活用した分子変換法の開発と天然物合成への応用 (2015)
  • Author(s): 安藤 吉勇
  • Organizer: 第３９回星薬科大学大学院研究科助手会・大学院自治会 合同公開セミナー
  • Place of Presentation: 星薬科大学 医薬品化学研究所 ５Ｆ 大谷ホール (東京都)
  • Year and Date: 2015-11-07
  • Invited
• [Presentation] Total Synthesis of (-)-spiroxin C (2015)
  • Author(s): Yoshio Ando, Atsuko Hanaki, Ryota Sasaki, Takashi Matsumoto, Ken Ohmori, Keisuke Suzuki
  • Organizer: ICCEOCA-10
  • Place of Presentation: 85 Sky Tower Hotel, Kaohsiung, Taiwan
  • Year and Date: 2015-11-04
  • Int'l Joint Research
• [Presentation] ナフトキノンの立体特異的な光酸化還元反応：スピロキシン類の不斉全合成 (2015)
  • Author(s): 安藤吉勇、花木淳子、佐々木亮太、松本隆司、大森建、鈴木啓介
  • Organizer: 第57回天然有機化合物討論会
  • Place of Presentation: 神奈川県民ホール (神奈川県)
  • Year and Date: 2015-09-10
• [Presentation] (-)-スピロキシンCの全合成研究 (2015)
  • Author(s): 安藤吉勇、花木淳子、大森建、鈴木啓介
  • Organizer: 日本化学会第９５春季年会
  • Place of Presentation: 千葉
  • Year and Date: 2015-03-28
• [Presentation] スピロキシンAの合成研究 (2015)
  • Author(s): 佐々木亮太、安藤吉勇、大森建、鈴木啓介
  • Organizer: 日本化学会第９５春季年会
  • Place of Presentation: 千葉
  • Year and Date: 2015-03-28
• [Remarks] Suzuki-Ohmori research group
  • URL: http://www.org-synth.chem.sci.titech.ac.jp/suzukilab/
• [Remarks] Suzuki–Ohmori Research Group
  • URL: http://www.org-synth.chem.sci.titech.ac.jp/suzukilab/