Development of new cycloaddition reactions with 1, 4-zwitterionic intermediates and application to synthesis of bioactive compounds

2011 Fiscal Year Final Research Report

• Project/Area Number: 21689001
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Chemical pharmacy
• Research Institution: Kanazawa University
• Principal Investigator: MATSUO Junichi 金沢大学, 薬学系, 准教授 (50328580)
• Project Period (FY): 2009 – 2011
• Keywords: 有機合成反応 / 環化付加 / 小員環化合物 / 全合成

Research Abstract

We found that formal[ 4+2] cycloaddition reactions of 3-ethoxycyclobutanones with allylsilanes, silyl enol ethers, imines, or indoles proceeded smoothly to afford the corresponding six-membered cyclic compounds in high yields by activating the cyclobutanones with appropriate Lewis acids. We accomplished total synthesis of(±)-bremazocine and(±)-aspidospermidine by using the new cycloaddition.

Research Products

• [Journal Article] Ring Cleavage and Successive Aldol Reaction of 3-[(Trialkylsilyl) methyl] cyclobutanones (2011)
  • Author(s): Jun-ichi Matsuo, Kosuke Harada, Mizuki Kawano, Ryosuke Okuno, and Hiroyuki Ishibashi
  • Journal Title: Org. Lett Volume: 13 Pages: 5986-5989
  • DOI: DOI:10.1021/ol202424p
  • Peer Reviewed
• [Journal Article] Asymmetric Synthesis of 2, 3-Dihydro-4-pyranones by Reaction of Chiral 3-Alkoxycyclobutanone and Aldehydes (2010)
  • Author(s): Shoko Negishi, Hiroyuki Ishibashi and Jun-ichi Matsuo
  • Journal Title: Org Lett Volume: 12 Pages: 4984-4987
  • DOI: DOI:10.1021/ol1021355
  • Peer Reviewed
• [Journal Article] Titanium(IV) Chloride-Mediated Carbon-. Carbon Bond-Forming Reaction Between 3, 3-Dialkylcyclobutanones and Aldehydes (2010)
  • Author(s): Jun-ichi Matsuo, Mizuki Kawano, Ryosuke Okuno, and Hiroyuki Ishibashi
  • Journal Title: Org. Lett Volume: 12 Pages: 3960-3962
  • DOI: DOI:10.1021/ol101653b
  • Peer Reviewed
• [Journal Article] A New Synthesis of 2, 3-Di-or 2, 3, 3-Trisubstituted 2, 3-Dihydro-4-pyridones by Reaction of 3-Ethoxycyclobutanones and N-p-Toluenesulfonyl Imines Using Titanium(IV) Chloride : Synthesis of(±)-Bremazocine (2010)
  • Author(s): Jun-ichi Matsuo, Ryohei Okado, and Hiroyuki Ishibashi
  • Journal Title: Org. Lett Volume: 12 Pages: 3266-3268
  • DOI: DOI:10.1021/ol1012313
  • Peer Reviewed
• [Journal Article] Intramolecular Formal[ 4+2] Cycloaddition of 3-Ethoxycyclobutanones and Alkenes (2010)
  • Author(s): Jun-ichi Matsuo, Shun Sasaki, Takaya Hoshikawa
  • Journal Title: Chem. Commun Volume: 46 Pages: 934-936
  • DOI: DOI:10.1039/B919332D
  • Peer Reviewed
• [Journal Article] Formal[ 4+2] cycloaddition between 3-ethoxycyclobutanones and silyl enol ethers (2009)
  • Author(s): Jun-ichi Matsuo, Shoko Negishi, and Hiroyuki Ishibashi
  • Journal Title: Tetrahedron Lett Volume: 50 Pages: 5831-5833
  • DOI: DOI:10.1016/j.tetlet.2009.08.013
  • Peer Reviewed
• [Journal Article] Tin(IV) Chloride-Catalyzed Cycloaddition Reactions Between 3-Ethoxycyclobutanones and Allylsilanes (2009)
  • Author(s): Jun-ichi Matsuo, Shun Sasaki, Takaya Hoshikawa, and Hiroyuki Ishibashi
  • Journal Title: Org. Lett Volume: 11 Pages: 3822-3825
  • DOI: DOI:10.1021/ol901329c
  • Peer Reviewed
• [Presentation] Synthetic study of strictamine by[ 4+2] cycloaddition between cyclobutanone and indole (2011)
  • Author(s): Shoko Negishi, Takaya Hoshikawa, Mio Hashizume, Jun-ichi Matsuo, and Hiroyuki Ishibashi
  • Organizer: 8th AFMC International Medicinal Chemistry Symposium
  • Place of Presentation: 東京都
  • Year and Date: 20111129-1202
• [Presentation] シクロブタノンとニトロンを用いる新規γ-ラクトン合成法の開発 (2011)
  • Author(s): 奥野良将、石橋弘行、松尾淳一
  • Organizer: 第41回複素環化学討論会
  • Place of Presentation: 熊本市民会館(熊本県)
  • Year and Date: 20111020-22
• [Presentation] Ring Cleavage and[ 4+2] Cycloaddition Reactions with Cyclobutanones (2011)
  • Author(s): Jun-ichi Matsuo
  • Organizer: Wesleyan University Seminar
  • Place of Presentation: CT(USA)
  • Year and Date: 2011-09-09
• [Presentation] 3-シリルメチルシクロブタノンとアルデヒドとのアルドール反応 (2011)
  • Author(s): 原田紘佑、河野瑞貴、石橋弘行、松尾淳一
  • Organizer: 日本薬学会第131年会
  • Place of Presentation: グランシップ(静岡県)
  • Year and Date: 2011-03-30
• [Presentation] Discovery of New Organic Reaction (2010)
  • Author(s): Jun-ichi Matsuo
  • Organizer: The 4^<th> Symposium Japan-France Frontier of Science
  • Place of Presentation: Poitier(France)
  • Year and Date: 20101121-24
• [Presentation] シクロブタノン環の開裂を伴うアルドール反応 (2010)
  • Author(s): 河野瑞貴、奥野良将、原田紘佑、松尾淳一、石橋弘行
  • Organizer: 第36回反応と合成の進歩シンポジウム
  • Place of Presentation: ウインクあいち(愛知県)
  • Year and Date: 2010-11-02
• [Presentation] 1, 4-双極性活性種の生成とその反応 (2010)
  • Author(s): 松尾淳一、佐々木俊、香西孝章、田中宏幸、根岸祥子、干川貴也、岡戸良平、石橋弘行
  • Organizer: 第97回有機合成シンポジウム
  • Place of Presentation: 慶応義塾大学薬学部(東京都)
  • Year and Date: 2010-06-19
• [Presentation] 3-エトキシシクロブタノンとイミンとの[ 4+2]環化付加反応の開発及び(±)-Bremazocineの合成 (2010)
  • Author(s): 岡戸良平、松尾淳一、石橋弘行
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山大学(岡山県)
  • Year and Date: 2010-03-28
• [Presentation] 1, 4-双極性活性種の生成と環化付加反応 (2010)
  • Author(s): 松尾淳一
  • Organizer: 第3回日本化学会東海支部若手研究者フォーラム
  • Place of Presentation: 名古屋大学(愛知県)
  • Year and Date: 2010-01-29
• [Remarks]
  • URL: http://www.p.kanazawa-u.ac.jp/~gousei/