Helical chirality of helicene that creates an effective asymmetric reaction field?

• Project/Area Number: 15K18835
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Chemical pharmacy
• Research Institution: Iwate Medical University
• Principal Investigator: Tsujihara Tetsuya 岩手医科大学, 薬学部, 助教 (10468316)
• Project Period (FY): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000); Fiscal Year 2016: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2015: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
• Keywords: ヘリセン / 不斉リン配位子 / Miyazaki-Newman-Kwart転位 / 硫黄官能基化ヘリセン / 光学分割 / チアヘリセン / 不斉触媒 / ヘリセンチオール / [7]チアヘリセン / ホスフィナイト / 不斉配位子 / パラジウム / 不斉アリル位アルキル化

Outline of Final Research Achievements

In this study, a helicene-based phosphinite ligands has been synthesized and its catalytic activity has been evaluated using the model reaction. Furthermore, the synthesis and optical resolution of helically chiral 1-sulfur-functionalized [6]helicene have been accomplished. A novel enantiopure [7]thiahelicene has also been synthesized.

Research Products

• [Journal Article] Nickel-Catalyzed Construction of Chiral 1-[6]Helicenols and Application in the Synthesis of [6]Helicene-Based Phosphinite Ligands (2016)
  • Author(s): Tsujihara, Tetsuya; Inada-Nozaki, N.; Takehara, T.; Zhou, D.-Y.; Suzuki, T.; Kawano, T.
  • Journal Title: European Journal of Organic Chemistry Volume: ー Issue: 29 Pages: 4948-4952
  • DOI: 10.1002/ejoc.201600677
  • Peer Reviewed
• [Journal Article] Efficient Enantioselective Synthesis of Oxahelicenes Using Redox/Acid Cooperative Catalysts (2016)
  • Author(s): Sako, Makoto; Takeuchi, Y.; Tsujihara, Tetsuya; Kodera, J.; Kawano, T.; Takizawa, S.; Sasai, H.
  • Journal Title: Journal of the American Chemical Society Volume: 138 Issue: 36 Pages: 11481-11484
  • DOI: 10.1021/jacs.6b07424
  • Peer Reviewed
• [Presentation] ヘリセン型不斉触媒創製を指向した1-[6]ヘリセンチオール誘導体の合成 (2017)
  • Author(s): 辻原哲也、佐々木歩美、遠藤沙耶香、山髙裕毅、鈴木健之、河野富一
  • Organizer: 日本薬学会第137年会
  • Place of Presentation: 東北大学（仙台）
  • Year and Date: 2017-03-27
• [Presentation] Vanadium (V)-Catalyzed Enantioselective Synthesis of Oxa[9]helicene (2016)
  • Author(s): Sako, Makoto; Takizawa, S.; Takeuchi, Y.; Tsujihara, Tetsuya; Ichinose, K.; Kodera, J.; Yoneyama, S.; Kawano, T.; Sasai, H.
  • Organizer: Molecular Chirality Asia 2016
  • Place of Presentation: Knowledge Capital Congres Convention Center (Osaka)
  • Year and Date: 2016-04-20
  • Int'l Joint Research
• [Presentation] ヘリセン型ホスフィナイト配位子の開発 (2015)
  • Author(s): 辻原哲也、野﨑奈央、城内亜沙子、佐藤ゆう美、鈴木健之、畠中 稔、河野富一
  • Organizer: 第54 回日本薬学会東北支部大会
  • Place of Presentation: 岩手医科大学（岩手・矢巾町）
  • Year and Date: 2015-09-26
• [Presentation] Ni 触媒を用いるアルキニルシクロヘキサジエノンの還元的環化反応 (2015)
  • Author(s): 佐藤成朗、岩渕杏子、留場守穂、辻原哲也、河野富一
  • Organizer: 第54 回日本薬学会東北支部大会
  • Place of Presentation: 岩手医科大学（岩手・矢巾町）
  • Year and Date: 2015-09-26