Highly efficient domino reaction of alkoxyimines bearing multiple bond

• Project/Area Number: 15K07877
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Kobe Pharmaceutical University
• Principal Investigator: Ueda Masafumi 神戸薬科大学, 薬学部, 准教授 (00340935)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2016: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: イソキサゾール / イソキサゾリジン / インドール / 金触媒 / 閉環反応 / 転位反応 / Fischer型インドール合成 / ハロ環化 / 付加環化反応 / 架橋型複素環 / ドミノ反応 / アルキン / アルコシキイミン / 共役ヒドラゾン / ヨウ化t-ブチル / インドール合成

Outline of Final Research Achievements

In order to develop novel synthetic methods for preparation of heterocyclic compounds, we investigated several domino reactions. Gold-catalyzed domino reaction of N-alkoxyimines and N-alkoxyamides bearing alkyne moiety via cyclization and rearrangement or cycloaddition provided 3-hydroxyisoxazoles and bridged isoxazolidines. Reductive Fischer indolization of conjugated hydrazones to give various indole derivatives been also developed.

Research Products

• [Journal Article] Triphosgene-Mediated Chlorolactamization and Aminolactamization of Homoallylic Amines (2017)
  • Author(s): Yuika Nishida, Norihiko Takeda, Okiko Miyata, and Masafumi Ueda
  • Journal Title: Heterocycles Volume: 95 Issue: 2 Pages: 787-798
  • DOI: 10.3987/com-16-s(s)42
  • Peer Reviewed
• [Journal Article] Regiodivergent Chlorine Atom-transfer Ring-opening Reaction of Trichloromethylcyclopropanes (2017)
  • Author(s): Nobuyoshi Doi, Norihiko Takeda, Okiko Miyata and Masafumi Ueda
  • Journal Title: Eur. J. Org. Chem. Volume: 2017 Issue: 25 Pages: 3652-3657
  • DOI: 10.1002/ejoc.201700567
  • Peer Reviewed
• [Journal Article] Nucleophilic Arylation of N,O-Ketene Acetals with Triaryl Aluminum Reagents: Access to α-Aryl Amides through an Umpolung Process (2017)
  • Author(s): Takeda Norihiko、Futaki Erika、Kobori Yukiko、Ueda Masafumi、Miyata Okiko
  • Journal Title: Angew. Chem. Int. Ed. Volume: 56 Issue: 51 Pages: 16342-16346
  • DOI: 10.1002/anie.201708665
  • Peer Reviewed
• [Journal Article] Gold-Catalyzed [3+2]/Retro-[3+2]/[3+2] Cycloaddition Cascade Reaction of N-Alkoxyazomethine Ylides (2017)
  • Author(s): Shoichi Sugita, Norihiko Takeda, Norimitsu Tohnai, Mikiji Miyata, Okiko Miyata and Masafumi Ueda
  • Journal Title: Angew. Chem. Int. Ed. Volume: 56 Issue: 9 Pages: 2469-2469
  • DOI: 10.1002/anie.201611816
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Gold-catalyzed Sequential Cyclization/rearrangement Reaction of O-Allyl Hydroxamates: Atom Economical Synthesis of 3-Hydroxyisoxazoles (2016)
  • Author(s): Shoichi Sugita, Masafumi Ueda, Nobuyoshi Doi, Norihiko Takeda and Okiko Miyata
  • Journal Title: Tetrahedron Lett. Volume: 57 Issue: 16 Pages: 1786-1789
  • DOI: 10.1016/j.tetlet.2016.03.032
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Regiodivergent Ring-Opening Reaction of Trichloromethylcyclopropane Carboxylates (2016)
  • Author(s): Nobuyoshi Doi, Norihiko Takeda, Okiko Miyata and Masafumi Ueda
  • Journal Title: J. Org. Chem. Volume: 81 Issue: 17 Pages: 7855-7861
  • DOI: 10.1021/acs.joc.6b01508
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Dimethylzinc-mediated Chlorolactamization of Homoallylic Amines with Chloroform. (2016)
  • Author(s): Yuika Nishida, Masafumi Ueda, Masataka Hayashi, Norihiko Takeda, Okiko Miyata.
  • Journal Title: Eur. J. Org. Chem. Volume: - Issue: 1 Pages: 22-25
  • DOI: 10.1002/ejoc.201501241
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] tert-Butyl Iodide-Mediated Reductive Fischer Indolization of Conjugated Hydrazones. (2016)
  • Author(s): Yuta Ito, Masafumi Ueda, Norihiko Takeda, Okiko Miyata.
  • Journal Title: Chem. Eur. J Volume: 22 Issue: 8 Pages: 2616-2619
  • DOI: 10.1002/chem.201504010
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] 窒素原子上にヘテロ原子をもつイミンおよびアミドの特性を活用したヘテロ環合成 (2018)
  • Author(s): 上田 昌史
  • Organizer: ヘテロ原子部会第３回懇話会
  • Invited
• [Presentation] Aminocarbonylation of homoallylic amines with chloroform (2017)
  • Author(s): Masafumi Ueda, Yuika Nishida, Norihiko Takeda, Okiko, Miyata
  • Organizer: 18th Tetrahedron Symposium
  • Int'l Joint Research
• [Presentation] 共役ヒドラゾンの求核性を利用したインドール類およびピラゾール類の合成 (2017)
  • Author(s): 上田 昌史、伊藤 勇太、野久保 名菜恵、八幡 茉由、武田 紀彦、宮田 興子
  • Organizer: 第47回複素環化学討論会
• [Presentation] N－アルコキシプロピルアミド類の閉環反応を基盤とするイソキサゾール合成 (2016)
  • Author(s): 杉田翔一、武田紀彦、宮田興子、上田昌史
  • Organizer: 第46回複素環化学討論会
  • Place of Presentation: 金沢
  • Year and Date: 2016-09-26
• [Presentation] クロロホルムをホスゲン等価体として用いるラクタム化およびカルバモイル化反応の開発 (2016)
  • Author(s): 西田唯香、武田紀彦、松野研司、宮田興子、上田昌史
  • Organizer: 第36回有機合成若手セミナー
  • Place of Presentation: 京都
  • Year and Date: 2016-08-06
• [Presentation] Gold-catalyzed cyclization-rearrangement reaction for the synthesis of 3-hydroxyisoxazoles (2016)
  • Author(s): Shoichi Sugita, Masafumi Ueda, Norihiko Takeda, Okiko Miyata
  • Organizer: 17th Tetrahedron Symposium
  • Place of Presentation: Sitges
  • Year and Date: 2016-06-30
  • Int'l Joint Research
• [Presentation] Gold-catalyzed sequential [3+2]/retro-[3+2] cycloadditions cascade of N-alkoxyazomethine ylide (2016)
  • Author(s): Masafumi Ueda, Shoichi Sugita, Norihiko Takeda, Okiko Miyata
  • Organizer: 17th Tetrahedron Symposium
  • Place of Presentation: Sitges
  • Year and Date: 2016-06-30
  • Int'l Joint Research
• [Presentation] ホモアリルアミン類とクロロホルムによる新規ラクタム化反応の開発 (2015)
  • Author(s): 上田昌史、西田唯香、河野友紀子、武田紀彦、宮田興子
  • Organizer: 第45回複素環化学討論会
  • Place of Presentation: 東京
  • Year and Date: 2015-11-19
• [Presentation] Gold-Catalyzed Generation of N-Alkoxyazometine Ylide and Cycloaddition Cascade (2015)
  • Author(s): Masafumi Ueda, Shoichi Sugita, Norihiko Takeda, Okiko Miyata
  • Organizer: The 13th International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: 京都
  • Year and Date: 2015-11-12
  • Int'l Joint Research
• [Presentation] ヨウ化水素の特性を利用した共役ヒドラゾンの還元反応の開発とインドール合成への応用 (2015)
  • Author(s): 伊藤勇太、上田昌史、武田紀彦、宮田興子
  • Organizer: 第41回反応と合成の進歩シンポジウム
  • Place of Presentation: 東大阪
  • Year and Date: 2015-10-27