Investigation of the rectivity of highly-strained sp-carbon atom in organometallic five-membered unsaturated molecules and its application

• Project/Area Number: 17K05791
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Sophia University
• Principal Investigator: Suzuki Noriyuki 上智大学, 理工学部, 教授 (90241231)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2019: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: 高歪み環状不飽和炭化水素 / ジルコニウム / 五員環アレン / アミド / 環状アレン / イソシアナート / 共役エンイン / カルベン / エステル / タンタル / 有機化学 / 有機金属化学 / 環状アルキン

Outline of Final Research Achievements

We recently developed novel organozirconium compounds that are have a five-membered cyclic allene structure. These compounds are surprisingly stable despite their highly strained structure, and were prepared from low-valent zirconium complexes and 1,3-enyne compounds. In this study, we investigated their property and reactivity on carbene-like character of center-carbon of the allene moiety. Nucleophilic addition of the unsaturated hydrocarbyl part to isocyanate esters, for example, afforded amide of allene moieties.

Academic Significance and Societal Importance of the Research Achievements

安定な五員環アレン化合物は2008年に代表者らが初めて報告したが、それまで五員環アレンは不安定で単離できないというのが有機化学の常識であった。それゆえこの化合物の性質、反応性についてはいまだに多く知られていない。この特異な構造を有する化合物についてつまびらかにすることは今後の構造有機化学的な理解の上で学術的な意義が大きい。さらにこれらの分子を種々の有機合成反応へ利用できる例を示したことにより、官能基を有する不飽和炭化水素の新たな合成方法を見出した点において社会的意義を有する

Research Products

• [Journal Article] Bilobalide and PC12 cells: A structure activity relationship study (2020)
  • Author(s): Usuki Toyonobu、Yoshimoto Yukiko、Sato Makiko、Takenaka Tae、Takezawa Ryota、Yoshida Yusuke、Satake Masayuki、Suzuki Noriyuki、Hashizume Daisuke、Dzyuba Sergei V.
  • Journal Title: Bioorganic & Medicinal Chemistry Volume: 28 Issue: 2 Pages: 115251-115251
  • DOI: 10.1016/j.bmc.2019.115251
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Palladium-catalyzed Mizoroki-Heck reactions in water using thermoresponsive polymer micelles (2019)
  • Author(s): Noriyuki Suzuki, Taiga Takabe, Yoshiko Yamauchi, Shun Koyama, Rina Koike, Masahiro Rikukawa, Wei-Ting Liao, Wen-Sheng Peng, Fu-Yu Tsai
  • Journal Title: Tetrahedron Volume: 75 Issue: 10 Pages: 1351-1358
  • DOI: 10.1016/j.tet.2019.01.047
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Five-membered Zircona- and Titanacycloallenes; Their Diverse Reactivity Depending upon The Position of Substituents (2018)
  • Author(s): Noriyuki Suzuki, Rikako Kurita, Akiko Kawamura, Tomoyuki Ono, Yoshiro Masuyama
  • Journal Title: Journal of Organometallic Chemistry Volume: 874 Pages: 40-48
  • DOI: 10.1016/j.jorganchem.2018.08.010
  • Peer Reviewed
• [Journal Article] Synthesis of O,N,O P multidentate ligands and the formation of early?late heterobimetallic complexes (2018)
  • Author(s): Suzuki Noriyuki、Yoneyama Satoru、Shiba Keisuke、Hasegawa Takeshi、Masuyama Yoshiro
  • Journal Title: Inorganica Chimica Acta Volume: 471 Pages: 355-363
  • DOI: 10.1016/j.ica.2017.11.027
  • Peer Reviewed
• [Presentation] Pd固定化温度応答性コポリマーミセルを用いる水中での触媒反応 (2020)
  • Author(s): 江原 望・小池 里奈・小山 諄・竹岡 裕子1・陸川 政弘・鈴木 教之・Tsai-Yu Hung・Fu-Yu Tsai
  • Organizer: 日本化学会第100春季年会
• [Presentation] ジルコノセン五員環アレン錯体を出発とするエステル・アミド類の合成 (2019)
  • Author(s): 望月菖里・小野智之・細谷誠・鈴木教之
  • Organizer: 第66回有機金属化学討論会
• [Presentation] Synthesis of O,N,O-P Multidentate Ligand And Heterobimetallic Complexes (2019)
  • Author(s): Taichi Nakayama, Keisuke Shiba and Noriyuki Suzuki
  • Organizer: The 2019 Asian Chemical Congress
  • Int'l Joint Research
• [Presentation] Palladium-Catalyzed Reactions in Water Using Thermoresponsive Polymer Micelles (2019)
  • Author(s): Shun Koyama, Rina Koike, Yoshiko Yamauchi, Taiga Takabe, Masahiro Rikukawa, Noriyuki Suzuki, Wei-Ting Liao, Wen-Sheng Peng, and Fu-Yu Tsai
  • Organizer: The 2019 Asian Chemical Congress
  • Int'l Joint Research
• [Presentation] 温度応答性ミセルを用いる水中でのMizoroki-Heck反応 (2019)
  • Author(s): 小山諄・小池里奈・山内淑子・高部大河・陸川政弘・鈴木教之・Wei-Ting Liao, Wen-Sheng Peng, Fu-Yu Tsai
  • Organizer: 第66回有機金属化学討論会
• [Presentation] Synthesis of heterobimetallic complex bearing O,N,O-N,N multidentate ligands (2018)
  • Author(s): Miyu Miyoshi, Keisuke Shiba, Noriyuki Suzuki
  • Organizer: 7th EuCheMS Conference on Nitrogen Ligands
  • Int'l Joint Research
• [Presentation] Synthesis of O,N,O-multidentate ligands bearing a nitrile and oxazole (2018)
  • Author(s): Nao Tsunoda, Koki Nanase, Tatsuki Shimamura, Noriyuki Suzuki
  • Organizer: 7th EuCheMS Conference on Nitrogen Ligands
  • Int'l Joint Research
• [Presentation] 塩化スズ(II)が触媒するFriedel-Crafts反応を利用したベンゾチオフェン環を含む芳香族置換アセンの合成 (2018)
  • Author(s): 齊藤 圭亮・塚本 一興・松崎 正幹・竹岡 裕子・陸川 政弘・増山 芳郎・鈴木 教之
  • Organizer: 第98回日本化学会春季年会
• [Presentation] 温度応答性コポリマーに固定化したSCSピンサー型パラジウム錯体を用いる水中溝呂木-Heck反応 (2018)
  • Author(s): 水野 大輔・陸川 政弘・鈴木 教之
  • Organizer: 第98回日本化学会春季年会
• [Presentation] イオン性親水鎖を有する温度応答性コポリマーに固定化したプロリンを用いる不斉有機反応 (2017)
  • Author(s): 水野 大輔、陸川 政弘、鈴木 教之
  • Organizer: 第7回CSJ化学フェスタ2017
• [Presentation] 温度応答性ポリマーミセルを反応場とする水中での有機反応 (2017)
  • Author(s): 山内 淑子、Wei-Ting Liao、陸川 政弘、Fu-yu Tsai、鈴木 教之
  • Organizer: 第7回CSJ化学フェスタ2017
• [Presentation] ジルコニウム五員環アレン錯体と銅塩のトランスメタル化反応を用いた共役エンインへの炭素－炭素結合生成反応 (2017)
  • Author(s): 小野智之、細谷 誠、増山芳郎、鈴木 教之
  • Organizer: 第64回有機金属化学討論会
• [Presentation] Reactions in Water using Thermo-Responsive Copolymer Micelles: L-Proline-catalyzed Asymmetric Aldol Reaction and Pd-catalyzed Mizoroki-Heck Reacion (2017)
  • Author(s): Noriyuki Suzuki
  • Organizer: International Symposium on Pure and Applied Chemistry (ISPAC) 2017
  • Int'l Joint Research / Invited
• [Presentation] 温度応答性ミセルを用いたる水中での有機反応 (2017)
  • Author(s): 山内 淑子・水野 大輔・陸川 政弘・鈴木 教之
  • Organizer: 第6回 JACI/GSCシンポジウム