Development of environmentally benign substitution reaction system

2011 Fiscal Year Final Research Report

• Project/Area Number: 21550145
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Environmental chemistry
• Research Institution: Tohoku University
• Principal Investigator: ASAO Naoki 東北大学, 原子分子材料科学高等研究機構, 教授 (60241519)
• Project Period (FY): 2009 – 2011
• Keywords: グリーンケミストリー

Research Abstract

Homogeneous gold-catalyzed nucleophilic substitution reaction was developed by use of ortho-alkynylbenzoic acid alkyl esters as alkylating agents. The reactions with alkanethiols proceeded smoothly to give alkyl sulfides in high yields. The reactions with silyl enol ethers produced alpha-alkylated silyl enol ethers. Treatment of the eliminated isochoumarin with base followed by DMC gave the starting materials in high yields. To conduct this reaction system with heterogeneous catalysts, catalytic properties of nanoporous gold have been investigated. This material exhibited remarkable catalytic activities in benzannulation and oxidation of organic silanes.

Research Products

• [Journal Article] From molecular catalysts to nanostructured materials skeleton catalysts (2012)
  • Author(s): Asao, N. ; Jin, T. ; Tanaka, S. ; Yamamoto, Y.
  • Journal Title: Pure Appl. Chem.
  • Peer Reviewed
• [Journal Article] Donor-acceptor dyes incorporating a stable dibenzosilole p-conjugated spacer for dye-sensitized solar cells (2012)
  • Author(s): Akhtaruzzaman, Md. ; Islam, A. ; Yang, F. ; Asao, N. ; Kwon, E. ; Singh, S. P. ; Han, L. ; Yamamoto, Y.
  • Journal Title: J. Mater. Chem. 22 Pages: 10771-10778
  • Peer Reviewed
• [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
  • 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
  • Peer Reviewed
• [Journal Article] A novel metal-free panchromatic TiO2 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
  • 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
  • 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] 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
  • 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
  • Peer Reviewed
• [Journal Article] Therapeutic Target for the Treatment of Psoriasis : A Chiral Feasibility Study with STA-21 (2011)
  • Author(s): Miyoshi, K. ; Takaishi, M. ; Nakajima, K. ; Ikeda, M. ; Kanda, T. ; Tarutani, M. ; Iiyama, T. ; Asao, N. ; DiGiovanni, J. ; Sano, S.
  • Journal Title: J. Invest. Dermatology Volume: 131 Pages: 108-117
  • Peer Reviewed
• [Journal Article] Nano-structured Materials Catalyst. Nanoporous Gold Catalyzed Oxidation of Organosilanes with Water (2010)
  • Author(s): Asao, N. ; Ishikawa, Y. ; Hatakeyama, N. ; Menggenbateer, Yamamoto, Y. ; Chen, M. ; Zhang, W. ; Inoue, A.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 49 Pages: 10093-10095
  • Peer Reviewed
• [Journal Article] Gold-catalyzed C-S bond formation from thiols (2010)
  • Author(s): Jean, M. ; Renault, J. ; van de Weghe, P. ; Asao, N.
  • Journal Title: Tetrahedron Lett. Volume: 51 Pages: 378-381
  • Peer Reviewed
• [Journal Article] CuX2-Mediated [4+ 2] benzannulation as a new synthetic tool for stereoselective construction of haloaromatic compounds (2009)
  • Author(s): Isogai, Y. ; Menggenbateer ; Khan, F. N. ; Asao, N.
  • Journal Title: Tetrahedron Volume: 65 Pages: 9575-9582
  • Peer Reviewed
• [Journal Article] Gold-catalyzed substitution reaction with ortho-alkynylbenzoic acid alkyl esters as an efficient alkylating agent (2009)
  • Author(s): Aikawa, H. ; Tago, S. ; Umetsu, K. ; Haginiwa, N. ; Asao, N.
  • Journal Title: Tetrahedron Volume: 65 Pages: 1774-1784
  • Peer Reviewed
• [Journal Article] Gold-catalyzed transesterification of ortho-alkynylbenzoic acid esters : a novel protecting group for alcohols and phenols (2008)
  • Author(s): Umetsu, K. ; Asao, N.
  • Journal Title: Tetrahedron Lett. Volume: 49 Pages: 7046-7049
  • Peer Reviewed
• [Journal Article] Silver-catalyzed synthesis of 1, 2-dihydroisoquinolines through direct addition of carbon pronucleophiles to ortho-alkynyl aldimines (2008)
  • Author(s): Asao, N. ; Yudha, S. S. ; Nogami, T. ; Yamamoto, Y.
  • Journal Title: Heterocycles Volume: 76 Pages: 471-483
  • Peer Reviewed
• [Journal Article] An efficient method for construction of tetrahydroisoquinoline skeleton via double cyclization process using ortho-vinylbenzaldehydes and amino alcohols : Application to the synthesis of (S)-cryptostyline II (2008)
  • Author(s): Umetsu, K. ; Asao, N.
  • Journal Title: Tetrahedron Lett. Volume: 49 Pages: 2722-2725
  • Peer Reviewed
• [Journal Article] Preparation of 1, 2-Dihydroxyisoquinolines by Three Component Reaction under Catalyst-Free Conditions (2008)
  • Author(s): Iso, K. Yudha S., S. ; Asao, N.
  • Journal Title: Synthesis Pages: 820-822
  • Peer Reviewed
• [Journal Article] AuCl-catalyzed reaction of ortho-alkynyl(oxo)benzene with benzenediazonium 2-carboxylate as a synthetic method of anthracene (2008)
  • Author(s): Sato, K. ; Menggenbateer ; Kubota, T. ; Asao, N.
  • Journal Title: Ttriptycene, and phthalazine derivatives, Tetrahedron Volume: 64 Pages: 787-796
  • Peer Reviewed
• [Presentation] Nanostructured Materials as Skeleton Catalysts for Molecular Transformations (2012)
  • Author(s): N. Asao
  • Organizer: International Scientific Forum of Young Scientists of Asian-Pacific Region
  • Place of Presentation: Far Eastern Federal University, Vladivostok, Russia.(Invited Lecture)
  • Year and Date: 20120514-17
• [Presentation] 多孔質金触媒を用いたヒドロシラン化合物とアルコールの酸化反応 (2012)
  • Author(s): 石川敬章, 畠山直也, 浅尾直樹, 山本嘉則, 陳明偉, 張偉, 井上明久
  • Organizer: 触媒討論会
  • Place of Presentation: 東京工業大学, 東京
  • Year and Date: 20120328-29
• [Presentation] ナノポーラスPdを非担持型固体金属触媒とするカップリング反応の開発 (2012)
  • Author(s): 田中信也, 金子哲朗, 浅尾直樹, 山本嘉則, 陳明偉, 張偉, 井上明久
  • Organizer: 触媒討論会
  • Place of Presentation: 東京工業大学, 東京
  • Year and Date: 20120328-29
• [Presentation] ナノポーラスPdを非担持型固体金属触媒とする分子変換反応の開発 (2012)
  • Author(s): 田中信也, 金子哲朗, 浅尾直樹, 山本嘉則, 陳明偉, 張偉, 井上明久
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学, 横浜
  • Year and Date: 20120325-28
• [Presentation] ナノポーラス金触媒を用いた芳香環形成反応 (2012)
  • Author(s): 孟根巴特尓, 浅尾直樹, 山本嘉則, 陳明偉, 張偉, 井上明久
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学, 横浜
  • Year and Date: 20120325-28
• [Presentation] 表面科学的手法によるナノポーラス金触媒上の有機化学反応の機構解明 (2012)
  • Author(s): 湊丈俊, 伊藤英輔, 石川敬章, 畠山直也, 伊藤隆, 原正彦, 金有洙, 浅尾直樹, 山本嘉則
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学, 横浜
  • Year and Date: 20120325-28
• [Presentation] ナノポーラス金触媒を用いたフロー系によるアルコールの酸素酸化反応 (2012)
  • Author(s): 畠山直也, 浅尾直樹, 山本嘉則, 陳明偉, 張偉, 井上明久
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学, 横浜
  • Year and Date: 20120325-28
• [Presentation] ナノポーラス金を触媒としたアルコールのシリル化反応 (2012)
  • Author(s): 石川敬章, 浅尾直樹, 山本嘉則, 陳明偉, 張偉, 井上明久
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学, 横浜
  • Year and Date: 20120325-28
• [Presentation] ジベンゾシロール誘導体を用いた色素増感太陽電池 (2012)
  • Author(s): 瀬谷洋平, Md. Akhtaruzzaman, Islam Ashraful, 浅尾直樹, 韓礼元, 山本嘉則
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学, 横浜
  • Year and Date: 20120325-28
• [Presentation] Optoelectronic Properties of Newly Synthesized Furan/Phenylene Co-oligomer Single Crystal (2012)
  • Author(s): H. Shang, S. Ikeda, K. Thangavel, H. Shimotani, K. Oniwa, T. Jin, U. Md. Akhtar, N. Asao, Y. Yamamoto, H. Tamura, I. Hamada, K. Tanigaki
  • Organizer: 日本物理学会2012年年次大会
  • Place of Presentation: 西宮
  • Year and Date: 20120324-27
• [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): N. Asao
  • Organizer: UCSB ICMR/CNSI and Tohoku University Joint Workshop
  • Place of Presentation: Santa Barbara, USA
  • Year and Date: 20120109-12
• [Presentation] Atomic defect control on titanium dioxide surface by scanning tunneling microscopy (2011)
  • Author(s): T. Minato, C.-L. Pang, S. Kajita, N. Asao, Y. Yamamoto, T. Nakayama, M. Kawai, Y. Kim
  • Organizer: International Symposium on Surface Science (ISSS-6)
  • Place of Presentation: Tokyo
  • Year and Date: 20111211-15
• [Presentation] Molecular transformation with nanoporous materials skeleton catalysts (2011)
  • Author(s): N. Asao
  • Organizer: 4th French Research Organizations-Tohoku University Joint Workshop on Frontier Materials and Processes (Frontier 2011)
  • Place of Presentation: Sendai.(Invited Lecture)
  • Year and Date: 20111204-07
• [Presentation] Nanoporous Gold as an Effective and Reusable Catalyst for Molecular Transformations (2011)
  • Author(s): N. Asao
  • Organizer: Tateshina Conference
  • Place of Presentation: Tateshina
  • Year and Date: 20111111-13
• [Presentation] ナノポーラス金触媒を用いた分子変換反応の開発 (2011)
  • Author(s): 浅尾直樹, 畠山直也, 石川敬章, 山本嘉則, 陳明偉, 張偉, 井上明久
  • Organizer: 日本金属学会2011年秋季大会
  • Place of Presentation: 沖縄
  • Year and Date: 20111107-09
• [Presentation] Integrated Aerobic Oxidation of Alcohols Catalyzed by Nanoporous Gold (2011)
  • Author(s): N. Asao, N. Hatakeyama, Y. Yamamoto
  • Organizer: 第7回集積有機合成国際シンポジウム(ISIS-7)
  • Place of Presentation: 神戸
  • Year and Date: 20111009-10
• [Presentation] 二酸化チタン表面欠陥の操作反応の機構解明 (2011)
  • Author(s): 湊丈俊, Pang C. L., 梶田晴司, 浅尾直樹, 山本嘉則, 中山隆, 川合真紀, 金有洙
  • Organizer: 日本物理学会2011年秋季大会
  • Place of Presentation: 富山
  • Year and Date: 20110921-24
• [Presentation] ナノポーラス金触媒による有機化学反応の機構解明 (2011)
  • Author(s): 湊丈俊, 伊藤英輔, 石川敬章, 畠山直也, 原正彦, 金有洙, 浅尾直樹, 山本嘉則
  • Organizer: 第5回分子科学討論会
  • Place of Presentation: 札幌
  • Year and Date: 20110920-23
• [Presentation] Nanoporous Gold-Catalyzed Oxidation of Organosilanes (2011)
  • Author(s): Y. Ishikawa, N. Hatakeyama, Menggenbateer, N. Asao, Y. Yamamoto, M. Chen, W. Zhang, A. Inoue
  • Organizer: 有機金属化学討論会
  • Place of Presentation: 名古屋大学, 名古屋
  • Year and Date: 20110907-09
• [Presentation] (2011)
  • Author(s): S. Tanaka, T. Kaneko, N. Asao, Y. Yamamoto, M. Chen, W. Zhang, A. Inoue
  • Organizer: 有機金属化学討論会
  • Place of Presentation: 名古屋大学, 名古屋
  • Year and Date: 20110907-09
• [Presentation] Nanoporous Metallic Materials as Effective Green Catalysts for Molecular Transformations (2011)
  • Author(s): N. Asao
  • Organizer: 14th Asian Chemical Congress 2011 (14 ACC)
  • Place of Presentation: Bangkok, Thailand.(Invited Lecture)
  • Year and Date: 20110905-08
• [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
• [Presentation] ナノポーラスPdを触媒とするHeck反応の開発 (2011)
  • Author(s): 金子哲朗, 浅尾直樹, 山本嘉則, 陳明偉, 張偉, 井上明久
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 神奈川大学, 横浜
  • Year and Date: 20110326-29
• [Presentation] ナノポーラス金触媒を用いたアルコールの酸素酸化反応 (2011)
  • Author(s): 畠山直也, 孟根巴特尓, 浅尾直樹, 山本嘉則, 陳明偉, 張偉, 井上明久
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 神奈川大学, 横浜
  • Year and Date: 20110326-29
• [Presentation] ナノポーラス金触媒を用いた有機シラン化合物の酸化反応 (2011)
  • Author(s): 石川敬章, 畠山直也, 孟根巴特尓, 浅尾直樹, 山本嘉則, 陳明偉, 張偉, 井上明久
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 神奈川大学, 横浜
  • Year and Date: 20110326-29
• [Presentation] ナノポーラスPdを触媒とする鈴木カップリング反応の開発 (2011)
  • Author(s): 田中信也, 浅尾直樹, 山本嘉則, 陳明偉, 張偉, 井上明久
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 神奈川大学, 横浜
  • Year and Date: 20110326-29
• [Presentation] 二酸化チタンの表面欠陥の原子レベルでの物性解明 (2011)
  • Author(s): 湊丈俊, PANG, C. L., 梶田晴司, 浅尾直樹, 山本嘉則, 中山隆, 川合真紀, 金有洙
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 神奈川大学, 横浜
  • Year and Date: 20110326-29
• [Presentation] ナノポーラスPdを固体金属触媒とするカップリング反応の開発 (2011)
  • Author(s): 田中信也, 浅尾直樹, 山本嘉則, 陳明偉, 張偉, 井上明久
  • Organizer: 第22回万有仙台シンポジウム
  • Place of Presentation: 仙台
  • Year and Date: 2011-12-19
• [Presentation] Oxidation of alcohols with molecular oxygen catalyzed by reusable nanoporous gold (2010)
  • Author(s): N. Asao, N. Hatakeyama, Menggenbateer, Y. Yamamoto, M. Chen, W. Zhang, A. Inoue
  • Organizer: PACIFICHEM 2010
  • Place of Presentation: Hawaii, USA
  • Year and Date: 20101215-20
• [Presentation] Gold-catalyzed functionalization of silyl enol ethers (2010)
  • Author(s): T. Kaneko, H. Aikawa, N. Asao
  • Organizer: PACIFICHEM 2010
  • Place of Presentation: Hawaii, USA
  • Year and Date: 20101215-20
• [Presentation] Gold-catalyzed dehydration of alcohols (2010)
  • Author(s): Y. Seya ; K. Umetsu ; N. Asao
  • Organizer: PACIFICHEM 2010
  • Place of Presentation: Hawaii, USA
  • Year and Date: 20101215-20
• [Presentation] Individual Hydrogen Desorption from Titanium Dioxide Surfaces (2010)
  • Author(s): T. Minato, C.-L. Pang, N. Asao, Y. Yamamoto, M. Kawai, Y. Kim
  • Organizer: Asian Conference on Nanoscience and Nanotechnology Joint Conference with RIKEN-Asian Research Network Symposium (AsiaNANO 2010)
  • Place of Presentation: Tokyo
  • Year and Date: 20101101-03
• [Presentation] 金触媒を用いたシリルエノールエーテルの官能基化手法の開発 (2010)
  • Author(s): 金子哲朗・相川春夫・浅尾直樹
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学, 大阪
  • Year and Date: 20100326-29
• [Presentation] Nanoporous Gold as an Effective Heterogeneous Catalyst for Molecular Transformations (2010)
  • Author(s): N. Asao, N. Hatakeyama, Y. Ishikawa, Menggenbateer, Y. Yamamoto, M. Chen, W. Zhang, A. Inoue
  • Organizer: WCU/AMS (POSTECH)-WPI/AIMR Joint Workshop
  • Place of Presentation: Pohang, Korea
  • Year and Date: 2010-06-18
• [Presentation] Gold-Catalyzed Functionalization of Silyl Enol Ethers (2009)
  • Author(s): N. Asao, H. Aikawa, T. Kaneko
  • Organizer: The 4th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-4)
  • Place of Presentation: Bangkok, Thailand
  • Year and Date: 20091129-1203
• [Presentation] 金触媒環拡大反応によるシクロブテン環合成法の開発 (2009)
  • Author(s): 久保田俊彦, 浅尾直樹
  • Organizer: 化学系学協会東北大会
  • Place of Presentation: 日本大学工学部, 郡山
  • Year and Date: 20090919-21
• [Presentation] Gold-catalyzed transesterification : ortho-alkynylbenzoyl group as a novel protecting group for alcohols (2009)
  • Author(s): K. Umetsu, T. Kaneko, N. Asao
  • Organizer: The 5th international conference on gold science, technology and its applications (GOLD 2009)
  • Place of Presentation: Heidelberg, Germany
  • Year and Date: 20090726-29