Environmentally friendly selectivity control of enyne metathesis utilizing hydrogen-bonding interaction

2013 Fiscal Year Final Research Report

• Project/Area Number: 23590012
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Tokyo University of Science (2013); Kumamoto University (2011-2012)
• Principal Investigator: IMAHORI Tatsushi 東京理科大学, 工学部, 講師 (90433515)
• Co-Investigator(Kenkyū-buntansha): KURIHAR Seiji 熊本大学, 大学院自然科学研究科(工), 教授 (50225265)
• Project Period (FY): 2011 – 2013
• Keywords: エン-インメタセシス / 置換基効果 / タンデム反応 / 選択性制御

Research Abstract

We found that an allylic hydroxy group can activate the adjacent olefin in Ru-alkylidene catalyzed enyne metathesis. The substituent effect could be switched ON/OFF by protection or non-protection of the hydroxy group. By using the switching of the substituent effect, direction control of tandem enyne metathesis of dienynes has been accomplished. The generality of the direction-controlled tandem enyne metathesis was proven by applying to various enyne compounds. Since mechanistic studies suggested that the activation effect of an allylic hydroxy group arises from hydrogen-bonding interaction between the substrate and catalyst, direction control of the tandem enyne metathesis by regulating the hydrogen-bonding interaction was investigated. In this stage, the distinct direction control has not been accomplished completely, but the possibility was shown.

Research Products

• [Journal Article] Phenylenediyne-linked Bis(arenol)s to Produce Benzodifuran-containing Condensed Heteroaromatic Ring System (2013)
  • Author(s): Furusawa Masaki, Tatsushi Imahor i, Kazunori Igawa, Katsuhiko Tomooka, Ryo Irie
  • Journal Title: Chem. Lett Volume: 42 Pages: 1134-1136
• [Journal Article] Base-catalyzed Schmittel Cycloisomerization of o-Phenylenediyne-linked Bis(arenol)s to Indeno[1,2-c]chromenes (2013)
  • Author(s): Furusawa Masaki, Kosuke Arita, Tatsushi Imahor i, Kazunori Igawa, Katsuhiko Tomooka, Ryo Irie
  • Journal Title: Tetrahedron Lett Volume: 54 Pages: 7107-7110
• [Journal Article] Asymmetric Synthesis of 2-Propylisofagoine Using Allylic Hydroxyl Group Accelerated Ring-closing (2012)
  • Author(s): Tatsuya Taguchi, Tatsushi Imahor i, Yuichi Yoshimura, Atsushi Kato, Isao Adachi, Masatoshi Kawahata, Kentaro Yamaguchi, and Hiroki Takahata
  • Journal Title: Enyne Metathesis Heterocycles Volume: 84 Pages: 929-944
• [Journal Article] An Alternative Approach to para-C-H Arylation of Phenol : Palladium-Catalyzed Tandemγ-Arylation/Aromatization of 2-Cyclohexen-1-one derivatives (2012)
  • Author(s): Tatsushi Imahor i, Toru Tokuda, Tatsuya Taguchi, Hiroki Takahata
  • Journal Title: Org. Lett Volume: 14 Pages: 1172-1175
• [Journal Article] Azobenzene-tethered Bis(trityl alcohol) as A Photoresponsive Cooperative Acid Catalyst for Morita-Bailis-Hillman reaction (2012)
  • Author(s): Tatsushi Imahor i, Ryo Yamaguchi, Seiji Kurihara
  • Journal Title: Chem.-Eur. J Volume: 18 Pages: 10802-10807
• [Journal Article] α-1-C-Butyl-1,4-dideoxy-1,4-imino-L-arabi nitol as a Second-Generation Iminosugar-Based Oral alfa-Glucosidase Inhibitor for Improving Postprandial Hyperglycemia (2012)
  • Author(s): Atsushi Kato, Erina Hayashi, Saori Miyauchi, Isao Adachi, Tatsushi Imahor i, Yoshihiro Natori, Yuichi Yoshimura, Robert J. Nash, Hideyuki Shimaoka, Izumi Nakagome, Jun Koseki, Shuichi Hirono, Hiroki Takahata
  • Journal Title: J. Med. Chem Volume: 55 Pages: 10347-10362
• [Journal Article] The Synthesis and Biological Evaluation of 1-C-Alkyl-L-arabinoiminofuranoses, a Novel Class ofα-Glucosidase Inhibitors Bioorg (2011)
  • Author(s): Yoshihiro Natori, Tatsushi Imahor i, Keiichi Murakami, Yuichi Yoshimura, Shinpei Nakagawa, Atsushi Kato, Isao Adachi, and Hiroki Takahata
  • Journal Title: Med. Chem. Lett Volume: 21 Pages: 738-741
• [Journal Article] Palladium(II)-catalyzed Aerobic Oxidative Tandem Cyclization of Enediyne-linked Bis(2-naphthol): Synthesis and Characterization of a New Oxa[7]helicene (2011)
  • Author(s): Ryo Irie, Akihiro Tanoue, Tatsushi Imahor i, Kazunobu Igawa, Taisuke Matsumoto, Katsuhiko Tomooka, Shinsuke Kikuta, Tatsuya Uchida, and Tsutomu Katsuki
  • Journal Title: Chem. Lett Volume: 40 Pages: 1343-1345
• [Presentation] 動的分子空間による分子触媒化学 (2014)
  • Author(s): 今堀龍志
  • Organizer: 東京大学大学院薬学研究科金井研究室コロキウム
  • Place of Presentation: 東京大学
  • Year and Date: 2014-06-07
• [Presentation] "動かして制御する"新しい分子触媒化学、熊本大学拠点形成研究B「ソフト溶液プロセスをベースとした階層的ナノ組織集積材料の創成」 (2013)
  • Author(s): 今堀龍志
  • Organizer: 主催第2回講演会
  • Place of Presentation: 熊本大学
  • Year and Date: 2013-12-18
• [Presentation] 基質-触媒間相互作用によるタンデムエン-インメタセシス反応の方向性自在制御 (2012)
  • Author(s): 今堀龍志、宇野亨、栗原清二、高畑廣紀
  • Organizer: 日本薬学会第132年会
  • Place of Presentation: 北海道大学
  • Year and Date: 2012-03-29
• [Presentation] 多環へテロ環化合物構築に向けた方向性自在制御タンデムエン−インメタセシス反応の開発 (2011)
  • Author(s): 今堀龍志、宇野亨、栗原清二、高畑廣紀
  • Organizer: 第41回複素環化学討論会
  • Place of Presentation: 熊本大学
  • Year and Date: 20111020-22
• [Presentation] 複合系の触媒機能制御発現を基盤とする効率的有機合成反応の開拓 (2011)
  • Author(s): 今堀龍志
  • Organizer: 有機合成化学協会九州山口支部平成24年度秋季講演会支部奨励賞受賞講演
  • Place of Presentation: 九州工業大学
  • Year and Date: 2011-11-29