リサイクルシステムを利用した環境調和型置換反応の開発

2011 Fiscal Year Annual Research Report

• Project/Area Number: 21550145
• Research Institution: Tohoku University
• Principal Investigator: 浅尾 直樹 東北大学, 原子分子材料科学高等研究機構, 教授 (60241519)
• Keywords: ナノ多孔質金 / 不均一系触媒 / 芳香環形成反応 / リサイクル

Research Abstract

本課題では、リサイクルシステムの構築を目指した環境調和型反応の開発を行っている。本年度はリサイクルシステムへの展開を指向した固体触媒の開発を行った。金銀合金薄膜から硝酸により銀のみを選択的に溶出させることで、ナノ多孔質構造を有する金を作成できることが知られている。この脱合金化の温度を調節すると、生じる細孔のサイズを数十ナノメートルから数百ナノメートルに制御することができる。そこで申請者はこの金属材料を用いた炭素骨格構築反応の開発を目指した。その結果、触媒量のこの金属材料存在下でオルト位にアルキニル基を有するベンズアルデヒド誘導体とアセチレン化合物を反応させると、α位にケトン官能基を有するナフタレン化合物を合成できることを見出した。本反応は以前申請者自身が均一系金触媒を用いて開発した反応であるが、本研究により不均一系のナノ多孔質金触媒によってもこの反応が進行することが明らかになった。興味深いことに、本触媒の細孔サイズによって触媒活性が異なり、孔径が30nm程度のものが一番触媒活性が高く、100nm程度になると触媒活性が極端に低下することがわかった。触媒は反応終了後にピンセットで取り出すことができるため生成物との分離が容易で、回収のためにろ過や遠心分離などの煩雑な操作を必要としない。また回収した触媒は再利用が可能であり、少なくとも3回の繰り返し実験では触媒活性の変化は全く見られなかった。以上の結果は、本触媒が炭素骨格構築のための触媒として有機合成上有用であることを示しており、今後より効率的なリサイクルシステムの開発を目指す上で貴重な知見となる。

Research Products

• [Journal Article] Aerobic oxidation of alcohols in the liquid phase with nanoporous gold catalysts (2012)
  • Author(s): Asao, N.; Hatakeyama, N.; Menggenbateer, Minato, T.; Ito, E.; Hara, M.; Kim, Y.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Chem.Commun. Volume: 48 Pages: 4540-4542
  • DOI: 10.1039/c2cc17245c
  • Peer Reviewed
• [Journal Article] Donor-acceptor Dyes Incorporating Stable Dibenzosilole π-Conjugated Spacer for Dye-sensitized Solar Cells (2012)
  • Author(s): Akhtaruzzaman, Md.; Seya, Y.; Asao, N.; Islam, A.; Kwon, E.; El-Shafei, A.; Han, L.; Yamamoto, Y.
  • Journal Title: J.Mater.Chem. Volume: (印刷中)
  • DOI: 10.1039/c2jm30978e
  • Peer Reviewed
• [Journal Article] Nanoporous Gold-Catalyzed [4+2] Benzannulation between ortho-Alkynylbenzaldehydes and Alkynes (2012)
  • Author(s): Asao, N.; Menggenbateer, Seya, Y.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Synlett Volume: 23 Pages: 66-69
  • DOI: 10.1055/s-0031-1289527
  • Peer Reviewed
• [Journal Article] Formation and properties of Au-based nanograined metallic glasses (2011)
  • Author(s): Chen, N. ; Frank, R. ; Asao, N. ; Louzguine-Luzgin, D. V. ; Sharma, P. ; Wang, J. Q. ; Xie, G. Q. ; Ishikawa, Y. ; Hatakeyama, N. ; Lin, Y. C. ; Esashi, M. ; Yamamoto, Y. ; Inoue, A.
  • Journal Title: Acta Mater. Volume: 59 Pages: 6433-6440
  • Peer Reviewed
• [Journal Article] A novel metal-free panchromatic TiO_2 sensitizer based on a phenylenevinylene-conjugated unit and an indoline derivative for highly efficient dye-sensitized solar cells (2011)
  • Author(s): Akhtaruzzaman, Md.; Islam, A.; Yang, F.; Asao, N.; Kwon, E.; Singh, S.P.; Han, L.; Yamamoto, Y.
  • Journal Title: Chem.Commun. Volume: 47 Pages: 12400-12402
  • DOI: 10.1039/c1cc15580f
  • Peer Reviewed
• [Journal Article] Reusable and Sustainable Nanostructured Skeleton Catalyst : Heck Reaction with Nanoporous Metallic Pd (PdNPore) as a Support, Stabilizer and Ligand Free Catalyst (2011)
  • Author(s): Kaneko, T.; Tanaka, S.; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Adv.Synth.Catal. Volume: 353 Pages: 2927-2932
  • DOI: 10.1002/adcs.201100358
  • Peer Reviewed
• [Journal Article] Gold-catalyzed alkylation of silyl enol ethers with ortho-alkynylbenzoic acid esters (2011)
  • Author(s): Aikawa, H.; Kaneko, T.; Asao, N.; Yamamoto, Y.
  • Journal Title: Beilstein J.Org.Chem. Volume: 7 Pages: 648-652
  • DOI: 10.3762/bjoc.7.76
  • Peer Reviewed
• [Journal Article] A nanostructured skeleton catalyst : Suzuki-coupling with a reusable and sustainable nanoporous metallic glass Pd-catalyst (2011)
  • Author(s): Tanaka, S.; Kaneko, T.; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Chem.Commun. Volume: 47 Pages: 5985-5987
  • DOI: 10.1039/c1cc10710k
  • Peer Reviewed
• [Presentation] Mechanism of organic chemical reactions on nano-porous gold (2012)
  • Author(s): T. Minato, E. Ito, Y. Ishikawa, N. Hatakeyama, M. Hara, Y. Kim, N. Asao, Y. Yamamoto
  • Organizer: Towards Reality in Nanoscale Materials V
  • Place of Presentation: Levi, Finland
  • Year and Date: 20120220-22
• [Presentation] Nanoporous materials as skeleton catalysts for molecular transformations (2012)
  • Author(s): Asao, N.
  • Organizer: UCSB ICMR/CNSI and Tohoku University Joint Workshop
  • Place of Presentation: Santa Barbara, USA(招待講演)
  • Year and Date: 20120110-20120112
• [Presentation] Atomic defect control on titanium dioxide surface by scanning tunneling microscopy (2011)
  • Author(s): Minato, T.; Pang, C.-L.; Kajita, S.; Asao, N.; Yamamoto, Y.; Nakayama, T.; Kawai, M.; Kim, Y.
  • Organizer: International Symposium on Surface Science (ISSS-6)
  • Place of Presentation: Tokyo, Japan
  • Year and Date: 20111211-20111215
• [Presentation] Molecular transformation with nanoporous materials skeleton catalysts (2011)
  • Author(s): Asao, N.
  • Organizer: Frontier Materials and Processes (Frontier 2011)
  • Place of Presentation: Sendai, Japan(招待講演)
  • Year and Date: 20111203-20111207
• [Presentation] Nanoporous Metals as Effective Catalysts for Molecular Transformations (2011)
  • Author(s): Asao, N.
  • Organizer: Tateshina Conference on Organic Chemistry 2011
  • Place of Presentation: Tateshina, Japan
  • Year and Date: 20111111-20111113
• [Presentation] Integrated Aerobic Oxidation of Alcohols Catalyzed by Nanoporous Gold (2011)
  • Author(s): Asao, N.; Hatakeyama, N.; Yamamoto, Y.
  • Organizer: The Seventh International Symposium on Integrated Synthesis (ISIS-7)
  • Place of Presentation: Kobe, Japan
  • Year and Date: 20111009-20111010
• [Presentation] Nanoporous Metallic Materials as Effective Green Catalysts for Molecular Transformations (2011)
  • Author(s): Asao, N.
  • Organizer: 14th Asian Chemical Congress 2011 (14 ACC)
  • Place of Presentation: Bangkok, Thailand(招待講演)
  • Year and Date: 20110905-20110908
• [Presentation] Aerobic Oxidation of Alcohols Catalyzed by Nanoporous Gold (2011)
  • Author(s): N. Hatakeyama, Menggenbateer, N. Asao, Y. Yamamoto, M. Chen, W. Zhang, A. Inoue
  • Organizer: 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
  • Year and Date: 20110724-28
• [Presentation] Nanoporous gold as a catalyst for the oxidation of organosilanes (2011)
  • Author(s): Y. Ishikawa, N. Hatakeyama, Menggenbateer, N. Asao, Y. Yamamoto, M. Chen, W. Zhang, A. Inoue
  • Organizer: 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
  • Year and Date: 20110724-28
• [Presentation] Nanostructured Skeleton Catalyst : Suzuki-coupling and Heck Reaction with Nanoporous Pd-catalyst as a Non-supported Catalyst (2011)
  • Author(s): S. Tanaka, T. Kaneko, N. Asao, Y. Yamamoto, M. Chen, W. Zhang, A. Inoue
  • Organizer: 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
  • Year and Date: 20110724-28
• [Presentation] Nanoporous Gold Catalyzed Benzannulation Reaction (2011)
  • Author(s): Menggenbateer, N. Asao, Y. Yamamoto, M. Chen, W. Zhang, A. Inoue
  • Organizer: 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
  • Year and Date: 20110724-28