Design of solid supported carbaborane catalyst with the aim of developing latent reactivity and reuse methods

• Project/Area Number: 23790034
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Chemical pharmacy
• Research Institution: Tokushima Bunri University
• Principal Investigator: YAMAMOTO Hirofumi 徳島文理大学, 薬学部, 准教授 (70461366)
• Project Period (FY): 2011 – 2013
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2013: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2012: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2011: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: カルバボラン / 不均一系触媒 / 1,3-ジエン環化反応 / リサイクル / 再利用 / 水銀トリフラート / タンデム環化反応 / カルバボラニル水銀クロライド / 銀トリフラート / トリエトキシシラン

Research Abstract

We developed a novel heterogeneous catalyst, solid supported carbaboranylmercuric triflate, with the aim of reutilizing it. This solid supported catalyst showed the remarkable reactivities for aryl allyl alcohol cyclization, cyclization of N-tosylanilinoallylic alcohols, regioselective cycloisomerization of aryl- and hetero-substituted 1,3-dienes, tandem carbocyclization, and etc. The workup of these reactions was very simple, as the catalyst was recovered by filtration of the reaction mixture through ordinary filter paper. Moreover, the recovered catalyst was reused without significant loss of activity at least 20 times. In the case of decreasing the activity of the recovered catalyst through the process of reuse, it could be reactivated via the reaction with 2N hydrochloric acid and then silver triflate.

Research Products

• [Journal Article] Novel inhibitor of bacterial sphingomyelinase, SMY-540, developed based on three-dimensional structure analysis (2014)
  • Author(s): Oda, H. Imagawa, R. Kato, K. Yabiku, T. Yoshikawa, T. Takemoto, H. Takahashi, H. Yamamoto, M. Nishizawa, J. Sakurai, M. Nagahama
  • Journal Title: J. Enzyme Inhib. Med. Chem. Volume: 29 Issue: 3 Pages: 1-8
  • DOI: 10.3109/14756366.2013.777717
  • Peer Reviewed
• [Journal Article] Yellow Pigments,Fomitellanols A and B, and Drimane Sesquiterpenoids Cryptoporic Acids P and Q from Fomitella fraxinea and Their Inhibitory Activity against COX and 5-LO. K. Yoshikawa (2013)
  • Author(s): K. Kouso, M. Shimomura, M. Tanaka, H. Yamamoto, H. Imagawa, S. Arihara, T. Hashimoto
  • Journal Title: Molecules Volume: 18 Pages: 4181-4191
• [Journal Article] Novel inhibitor of bacterial sphingomyelinase, SMY-540, developed based on three-dimensional structure analysis (2013)
  • Author(s): M. Oda, H. Imagawa, R. Kato, K. Yabiku, T. Yoshikawa, T. Takemoto, H. Takahashi, H. Yamamoto, M. Nishizawa, J. Sakurai, M. Nagahama. J. Enzym
  • Journal Title: Inhib. Med. Chem Volume: (Ahead of Print) Pages: 1-8
• [Journal Article] Concise Synthesis of a Probe Molecule Enabling Analysis and Imaging of Vizantin (2013)
  • Author(s): H. Yamamoto, M. Oda, M. Nakano, K. Yabiku, M. Shibutani, T. Nakanishi, M. Suenaga, M. Inoue, H. Imagawa, M. Nagahama, Y. Matsunaga, S. Himeno, K. Setsu, J. Sakurai, M. Nishizawa
  • Journal Title: Chem. Pharm. Bull Volume: 61 Pages: 452-459
  • NAID: 130003360757
• [Journal Article] Development of Vizantin, a Safe Immunostimulant, based on the Structure-Activity Relationship of Trehalose-6,6'-Dicorynomycolate (2013)
  • Author(s): Yamamoto, H.; Oda, M.; Nakano, M.; Watanabe, N.; Yabiku, K.; Shibutani, M.; Inoue, M.; Imagawa, H.; Nagahama, M.; Himeno, S.; Setsu, K.; Sakurai, J.; Nishizawa, M
  • Journal Title: J. Med. Chem Volume: 56 Pages: 381-385
• [Journal Article] Yellow pigments, fomitellanols A and B, and drimane sesquiterpenoids, cryptoporic acids P and Q, from fomitella fraxinea and their inhibitory activity against COX and 5-LO (2013)
  • Author(s): K. Yoshikawa, K. Koso, M. Shimomura, M. Tanaka, H. Yamamoto, H. Imagawa, S. Arihara, T. Hashimoto
  • Journal Title: Molecules Volume: 18 Issue: 4 Pages: 4181-4191
  • DOI: 10.3390/molecules18044181
  • Peer Reviewed
• [Journal Article] Concise Synthesis of a Probe Molecule Enabling Analysis and Imaging of Vizantin (2013)
  • Author(s): H. Yamamoto, M. Oda, M. Nakano, K. Yabiku, M. Shibutani, T. Nakanishi, M. Suenaga, M. Inoue, H. Imagawa, M. Nagahama, Y. Matsunaga, S. Himeno, K. Setsu, J. Sakurai, M. Nishizawa.
  • Journal Title: Chemical and Pharmaceutical Bulletin Volume: 61 Issue: 4 Pages: 452-459
  • DOI: 10.1248/cpb.c13-00006
  • NAID: 130003360757
  • ISSN: 0009-2363, 1347-5223
  • Peer Reviewed
• [Journal Article] Development of vizantin, a safe immunostimulant, based on the structure－activity relationship of trehalose-6,6′-dicorynomycolate (2013)
  • Author(s): H. Yamamoto, M. Oda, M. Nakano, N. Watanabe, K. Yabiku, M. Shibutani, M. Inoue, H. Imagawa, M. Nagahama, S. Himeno, K. Setsu, J. Sakurai, M. Nishizawa
  • Journal Title: J. Med. Chem Volume: 56 Issue: 1 Pages: 381-385
  • DOI: 10.1021/jm3016443
  • Peer Reviewed
• [Journal Article] A Carbaboranylmercuric Salt-Catalyzed Reaction; Highly Regioselective Cycloisomerization of 1,3-Die- nes (2012)
  • Author(s): Yamamoto, H.; Sasaki, I.; Shiomi, S.; Yamasaki, N.; Imagawa, H
  • Journal Title: Org. Lett Volume: 14 Pages: 2266-2269
• [Journal Article] Carbon-Nitrogen Bond Forming Reaction between Allyl Silyl Ether and Hydrazide Promoted by Mercuric Triflate Catalyst (2012)
  • Author(s): H. Yamamoto, N. Yamasaki, S. Yoshidome, I. Sasaki, K. Namba, H. Imagawa, M. Nishizawa
  • Journal Title: Synlett Pages: 1069-1073
• [Journal Article] Syntheses of Stracturally-simplified and Fluore- scently-labeled Neovibsanin Derivatives and Analysis of their Neurite Outgrowth Activity in PC12 cells (2012)
  • Author(s): H. Imagawa, H. Saijo, H. Yamaguchi, K. Maekawa, T. Kurisaki, H. Yamamoto, M. Nishizawa, M. Oda, M. Kabura, M. Nagahama, J. Sakurai, M. Kubo, M. Nakai, K. Makino, M. Ogata, H. Takahashi, Y. Fukuyama
  • Journal Title: Bioorg. Med. Chem. Lett Volume: 22 Pages: 2089-2093
• [Journal Article] A Carbaboranylmercuric Salt Catalyzed Reaction; Highly Regioselective Cycloisomerization of 1,3-Dienes (2012)
  • Author(s): Η. Yamamoto, I. Sasaki, S. Shiomi, N. Yamasaki, H. Imagawa
  • Journal Title: Org. Lett. Volume: 14 Issue: 9 Pages: 2266-2269
  • DOI: 10.1021/ol300678r
  • Peer Reviewed
• [Journal Article] Carbon-nitrogen bond formation between allyl silyl ether and hydrazide promoted by mercuric triflate catalyst, (2012)
  • Author(s): H. Yamamoto, N. Yamasaki, S. Yoshidome, I. Sasaki, K. Namba, H. Imagawa, M. Nishizawa,
  • Journal Title: Synlett Volume: 23 Issue: 07 Pages: 1069-1073
  • DOI: 10.1055/s-0031-1290758
  • Peer Reviewed
• [Journal Article] Syntheses of Structurally-simplified and Fluorescently-labeled Neovibsanin Derivatives and Analysis of their Neurite Outgrowth Activity in PC12 Cells. (2012)
  • Author(s): H.Imagawa, H. Siajo, H. Yamaguchi, K. Maekwa, T. Kurisaki, H. Yamamoto, M. Nishizawa, M. Oda, M. Kaubura, M. Nagahama, J. Sakurai, M. Nakai, K. Makino, M. Ogata, H. Takahashi, Y. Fukuyama
  • Journal Title: Bioorg. Med. Chem. Lett. Volume: 22,(5) Issue: 5 Pages: 2089-2093
  • DOI: 10.1016/j.bmcl.2012.01.006
  • Peer Reviewed
• [Journal Article] An Efficient Pyrrole Synthesis via Silaphenyme- rcuric Triflate-Catalyzed Cyclization of Homopro- pargyl Azides (2011)
  • Author(s): H. Yamamoto, I. Sasaki, M. Mitsutake, A. Karasudani, H. Imagawa, M. Nishizawa
  • Journal Title: Synlett Pages: 2815-2818
• [Journal Article] An Efficient Pyrrole Synthesis via Silaphenymercuric Triflate-Catalyzed Cyclization of Homopropargyl Azides. (2011)
  • Author(s): H. Yamamoto, I. Sasaki, M. Mitsutake, A. Karasudani, H. Imagawa, M. Nishizawa
  • Journal Title: Synlett Volume: 19 Issue: 19 Pages: 2815-2818
  • DOI: 10.1055/s-0031-1289566
  • Peer Reviewed
• [Presentation] 不均一系カルボラン水銀トリフラートを用いた1,3-ジエン環化反応 (2013)
  • Author(s): 山本博文
  • Organizer: 日本薬学会第133年会
  • Place of Presentation: パシフィコ横浜
• [Presentation] 水銀トリフラート触媒炭素―窒素結合形成反応の開発 : N-アシルN'-トシルヒドラジドの活用
  • Organizer: 日本薬学会第134年会
  • Place of Presentation: 熊本
• [Presentation] 不均一系カルボラン水銀トリフラートを用いた1,3-ジエン環化反応
  • Organizer: 日本薬学会第133年会
  • Place of Presentation: 横浜
• [Presentation] カルボラン架橋型不均一系触媒を用いた1,3-ジエン環化反応の開発
  • Organizer: 文部省戦略的研究基盤形成支援事業第9回研究報告会
  • Place of Presentation: 札幌
• [Presentation] 日本薬学会第132年会
  • Organizer: ホウ素クラスターを架橋分子とした新規固相水銀触媒の開発
  • Place of Presentation: 札幌
• [Presentation] ホウ素クラスターを架橋分子とした新規固相水銀触媒の開発
  • Author(s): 山本博文
  • Organizer: 日本薬学会第132年会
  • Place of Presentation: 北海道大学
• [Remarks] 徳島文理大学薬学部薬品製造学教室 ホームページ
  • URL: http://p.bunri-u.ac.jp/lab04/
• [Remarks] 徳島文理大学薬学部 薬品製造学教室 発表論文
  • URL: http://p.bunri-u.ac.jp/lab04/styled-4/index.html
• [Remarks] 徳島文理大学薬学部 薬品製造学教室 発表論文
  • URL: http://p.bunri-u.ac.jp/lab04/styled-4/index.html