Development of Helically Chiral Polymers Based on the Condensation of Arylboronic Acids with Diamines

• Project/Area Number: 24750105
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Polymer chemistry
• Research Institution: Kyoto University
• Principal Investigator: YAMAMOTO Takeshi 京都大学, 工学(系)研究科(研究院), 助教 (20624349)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2014: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2013: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2012: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: 合成化学 / らせん / Ｃ－Ｈ活性化 / ボリル化 / オリゴアレーン / 保護基 / 配向基 / C-H活性化 / オリゴナフタレン / 高分子合成 / 高分子構造・物性 / らせん不斉

Outline of Final Research Achievements

In this study, we established precise synthesis and helical chirality induction of ortho-linked oligo(naphthalene-2,3-diyl)s. Oligo(naphthalene-2,3-diyl)s with a terminal boronyl group were synthesized by iterative Suzuki-Miyaura cross-coupling of 3-iodo-2-naphthylboronic acid bearing 1,8-diaminonaphthalene as a protecting group on the boron atom. Hydrolysis of the protecting group and subsequent condensation with chiral diols gave helically chiral oligo(naphthalene-2,3-diyl)s. Furthermore, using 2-pyrazolylaniline as a removable directing group on the boron atom, we developed an efficient synthetic method for 1,2-diboryl arenes via iridium-catalyzed aromatic ortho-C-H borylation of arylboronic acids.

Research Products

• [Presentation] Ir-Catalyzed ortho-C－H Borylation of Arylboronic Acids Masked by Removable Directing Group on the Boron Atom (2015)
  • Author(s): Aoi Ｉｓｈｉｂａｓｈｉ, Takeshi Yamamoto, Michinori Suginome
  • Organizer: 日本化学会 第95春季年会
  • Place of Presentation: 本大学 理工学部船橋キャンパス
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] Boron-Masking Strategies for the Ｓynthesis of Helically Chiral Oligo（naphthalene-2,3-diyl）s (2014)
  • Author(s): Aoi Ｉｓｈｉｂａｓｈｉ, Takeshi Yamamoto, Michinori Suginome
  • Organizer: IＭＥＢＯＲＯＮ XV
  • Place of Presentation: Prague, Czech Republic
  • Year and Date: 2014-08-24 – 2014-08-28
• [Presentation] 光学活性ホウ素末端を有するオリゴ（ナフタレン-2，3-ジイル）の反復鈴木－宮浦カップリングによる合成とキラル高次構造制御 (2014)
  • Author(s): 石橋 葵・山本 武司・杉野目 道紀
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] らせん状分子の精密合成を指向した反復鈴木－宮浦カップリングによるオリゴ（ナフタレン-2，3-ジイル）の合成 (2013)
  • Author(s): 石橋 葵・山本 武司・杉野目 道紀
  • Organizer: 第60回有機金属化学討論会
  • Place of Presentation: 学習院大学
• [Presentation] Synthesis of Oligo（naphthalene-2，3-diyl）s by Iterative Suzuki-Miyaura Cross-Coupling with 1，8-Diaminonaphthalene-Masked 3-Iodo-2-naphtylboronic Acids (2013)
  • Author(s): Aoi Ishibashi， Masashi Koyanagi， Nils Eichenauer， Hideki Ihara， Takeshi Yamamoto， Michinori Suginome
  • Organizer: The Sixteenth International Symposium on Relations between Homogeneous and Heterogeneous Catalysis （ISHHC-16）
  • Place of Presentation: Sapporo， Japan
• [Presentation] Iterative Suzuki-Miyaura Cross-Coupling of B-Masked 3-Iodo-2- naphthylboronic Acids Directed Toward New Helical Architecture (2013)
  • Author(s): Aoi Ishibashi， Takeshi Yamamoto and Michinori Suginome
  • Organizer: 17th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis （OMCOS 17）
  • Place of Presentation: Fort Collins， CO， USA
• [Presentation] ホウ素上を保護した３-ヨード-２-ナフチルボロン酸をカップリングモジュールとする繰り返し鈴木‐宮浦カップリングによるオリゴ（ナフタレン-2，3-ジイル）の合成 (2013)
  • Author(s): 石橋 葵・小柳 雅史・EICHENAUER Nils・井原 秀樹・山本 武司・杉野目 道紀
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス
• [Remarks] The Suginome Research Group
  • URL: http://www.sbchem.kyoto-u.ac.jp/suginome-lab/