Challenge toward controlling oxidative phenol coupling reaction by AZADO-Cu cooperative catalysis

• Project/Area Number: 16K15096
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Chemical pharmacy
• Research Institution: Tohoku University
• Principal Investigator: Iwabuchi Yoshiharu 東北大学, 薬学研究科, 教授 (20211766)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2017: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2016: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: 触媒・化学プロセス / 協奏触媒 / 空気酸化 / フェノール酸化 / 精密有機合成 / 有機ニトロキシルラジカル / 酸化的カップリング / フェノール

Outline of Final Research Achievements

On the basis of our original aerobic catalytic alcohol oxidation system consisting of AZADO/CuCl/bipyridy/DMAP, we have challenged to discover another catalytic system that enables highly chemo- and regioselective phenol coupling reactions. As a result, we identified that combination of AZADO-Cr promoted an intramolecular coupling of 3-(3-(4-hydroxyphenyl)propyl)phenol to give the corresponding tricyclic product. We also disclosed that AZADO/CuCl/bipyridyl/DMAP system realized a highly chemoselective aerobic oxidation of sulfide-containing alcohols, providing a useful addition to AZADO oxidation technology.

Research Products

• [Presentation] ニトロキシルラジカル/銅協働触媒を用いる高化学選択的アルコール空気酸化反応：条件最適化と基質適用性拡張 (2018)
  • Author(s): 笹野 裕介、小暮 直貴、長澤 翔太、笠畑 洸希、岩渕 好治
  • Organizer: 第２８回万有仙台シンポジウム
• [Presentation] ニトロキシルラジカル/銅協働触媒を用いる高化学選択的アルコール空気酸化反応 (2018)
  • Author(s): 笹野裕介・長澤翔太・小暮直貴・Jaiwook Park・岩渕好治
  • Organizer: 第64回有機金属化学討論会
• [Presentation] Highly Chemoselective Aerobic Alcohol Oxidation Using AZADO-Copper Catalysis (2018)
  • Author(s): Yoshiharu Iwabuchi
  • Organizer: the 3rd Junior Advanced Research Network on Cutting-Edge Organic Chemistry in Asia
  • Int'l Joint Research / Invited
• [Presentation] 不斉配位子複合型ニトロキシルラジカル/銅協働触媒を用いるラセミ第2級アルコール の酸化的速度論的光学分割 (2018)
  • Author(s): 笹野裕介，小暮直貴，笠畑洸希，西山智弘，川島恭平，森聖治，岩渕好治
  • Organizer: 第43回反応と合成の進歩シンポジウム
• [Presentation] 三座配位型キラルAZADO/銅触媒系を用いたラセミ第二級アルコールの空気酸化的速度論的光学分割反応(OKR)の開発 (2018)
  • Author(s): 笠畑 洸希, 笹野 裕介, 小暮 直貴, 岩渕 好治
  • Organizer: 日本薬学会第138回年会
• [Presentation] AZADO/Cu触媒系を用いた含硫黄アルコールの高化学選択的空気酸化反応の開発 (2017)
  • Author(s): 小暮直貴、長澤翔太、笹野裕介、岩渕好治
  • Organizer: 日本薬学会第137年会
  • Place of Presentation: 東北大学
  • Year and Date: 2017-03-25
• [Presentation] AZADO-CuCl/bpy/DMAP/Air Enables Highly Efficient Oxidation of Amino Alcohols to Amino Carbonyl Compounds (2016)
  • Author(s): Iwabuchi, Y.; Sasano, Y.; Nagasawa, S.; Kogure, N.; Shibuya, M.
  • Organizer: The International Symposium on Homogeneous Catalysis (ISHC XX)
  • Place of Presentation: 京都テルサ
  • Year and Date: 2016-07-10
  • Int'l Joint Research
• [Presentation] AZADO-Cu/bpy/DMAP/Air Enables highly Chemoselective Oxidation of Amino Alcohols to Amino Carbonyl Compounds (2016)
  • Author(s): Iwabuchi, Y.; Sasano, Y.; Nagasawa, S.; Kogure, N.; Shibuya, M.
  • Organizer: The 25th French-Japanese Symposium on Medicinal and Fine Chemistry
  • Place of Presentation: 京王多摩プラザ
  • Year and Date: 2016-05-15
  • Int'l Joint Research
• [Remarks] 東北大学大学院薬学研究科合成制御化学分野ホームページ
  • URL: http://www.pharm.tohoku.ac.jp/~gousei/synthetic/index.html