Development of new catalysts utilizing cationic heterocyclic compounds as electron withdrawing groups

• Project/Area Number: 26810063
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: Meijo University
• Principal Investigator: Nishikawa Yasuhiro 名城大学, 薬学部, 助教 (20633580)
• Project Period (FY): 2014-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000); Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2014: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: 有機触媒 / ブレンステッド酸 / Diels-Alder反応 / 不斉合成 / キラルブレンステッド酸 / Diets-Alder反応

Outline of Final Research Achievements

Chiral pyridinium phosphoramide was designed and synthesized to be a dual acid catalyst in which both the pyridinium proton and the adjacent imide-like proton activated by the cationic pyridinium moiety could work cooperatively as strong dual proton donors. The dual acid catalyst was successfully used for the asymmetric cycloaddition reaction between 1-amidedienes and maleimides to afford a variety of compounds in highly stereoselective manners.

Research Products

• [Journal Article] Chiral Pyridinium Phosphoramide as Dual Brønsted Acid Catalyst for Enantioselective Diels-Alder Reaction (2016)
  • Author(s): Yasuhiro Nishikawa, Saki Nakano, Yuu Tahira, Kanako Terazawa, Ken Yamazaki, Chitoshi Kitamura and Osamu Hara
  • Journal Title: Organic Letters Volume: 18 Issue: 9 Pages: 2004-2007
  • DOI: 10.1021/acs.orglett.6b00608
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Pd(II)-Catalyzed Allylic C－H Amination for the Preparation of 1,2- and 1,3-Cyclic Ureas (2015)
  • Author(s): Y. Nishikawa, S. Kimura, Y. Kato, N. Yamazaki, O. Hara
  • Journal Title: Organic Letters Volume: 17 Issue: 4 Pages: 888-891
  • DOI: 10.1021/ol5037453
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] キラルピリジルリン酸アミド触媒を用いる不斉ブロモラクトン化反応の開発 (2016)
  • Author(s): 西川泰弘、濱本裕太、佐藤里佳、野本万里名、原 脩
  • Organizer: 日本薬学会136年会
  • Place of Presentation: 横浜
  • Year and Date: 2016-03-28
• [Presentation] 分子内アリル位C-Hアミノ化反応の立体選択性 (2016)
  • Author(s): 久世恵梨子、八橋有香里、松原千夏、前川紗矢香、西川泰弘、原 脩
  • Organizer: 日本薬学会136年会
  • Place of Presentation: 横浜
  • Year and Date: 2016-03-28
• [Presentation] Tetraethylorthosilicate as a Mild Dehydrating Reagent for the Synthesis of N-Formamides with Formic acid (2015)
  • Author(s): Kana Matsuda, Yasuhiro Nishikawa, Norimitsu Ukai, Hidetsugu Nakamura, Wakana Adachi, Rika Sato, Shohei Moriguchi, Osamu Hara
  • Organizer: The 2015 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2015-12-19
  • Int'l Joint Research
• [Presentation] Stereoselective construction of tetrahydropyrimidinone derivatives with intramolecular allylic C-H amination (2015)
  • Author(s): Yasuhiro Nishikawa, Akihiro Ito, Yuri Kato, Sayaka Maegawa, Yukari Yatsuhashi, Erika Niwa, Eriko Kuze, Osamu Hara
  • Organizer: The 2015 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2015-12-19
  • Int'l Joint Research
• [Presentation] Stereoselective construction of imidazolidinone derivatives with intramolecular allylic C-H amination (2015)
  • Author(s): Yasuhiro Nishikawa, Hiroto Tsurumi, Seiko Kimura, Natsuka Yamazaki, Naho Akada, Osamu Hara
  • Organizer: The 2015 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2015-12-19
  • Int'l Joint Research
• [Presentation] Direct coupling of oxazoline ring with aryl halides for the preparation of chiral oxazoline-containing ligands (2015)
  • Author(s): Yasuhiro Nishikawa, Shunsuke Kawaguchi, Kohei Takemoto, Takahiro Ishiguro, Kentaro Miwa, Osamu Hara
  • Organizer: The 2015 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2015-12-19
  • Int'l Joint Research
• [Presentation] 二座配位型キラルブレンステッド酸触媒の開発と不斉合成への応用 (2015)
  • Author(s): 西川泰弘、山崎 研、野本万里名、中野佐紀、田平 優、寺澤可奈子、原 脩
  • Organizer: 第41回反応と合成の進歩シンポジウム
  • Place of Presentation: 大阪
  • Year and Date: 2015-10-27
• [Presentation] キラルピリジルリン酸アミド触媒による不斉ブロモラクトン化反応の開発 (2015)
  • Author(s): 西川泰弘、野本万里名、濱本裕太、原 脩
  • Organizer: 第61回日本薬学会東海支部大会
  • Place of Presentation: 名古屋
  • Year and Date: 2015-07-04
• [Presentation] Direct coupling of chiral oxazolines with aryl halides and heteroaryl halides (2015)
  • Author(s): Osamu Hara, Takahiro Ishiguro, Kentaro Miwa, Kohei Takemoto and Yasuhiro Nishikawa
  • Organizer: 16th TETRAHEDRON SYMPOSIUM
  • Place of Presentation: Berlin, Germany
  • Year and Date: 2015-06-18
  • Int'l Joint Research
• [Presentation] 二座配位型キラルブレンステッド酸触媒による不斉Diels-Alder反応の開発 (2014)
  • Author(s): 西川泰弘、中野佐紀、田平優、寺澤可奈子、山崎研、原脩
  • Organizer: 第45回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 愛知
  • Year and Date: 2014-11-30
• [Presentation] 二座配位型キラルブレンステッド酸触媒による不斉Diels-Alder反応の開発 (2014)
  • Author(s): 西川泰弘、中野佐紀、田平優、寺澤可奈子、山崎研、原脩
  • Organizer: 第40回反応と合成の進歩シンポジウム
  • Place of Presentation: 仙台
  • Year and Date: 2014-11-11
• [Remarks] 機能分子化学研究室ホームページ
  • URL: http://lab-fmc-meijo.jimdo.com
• [Patent(Industrial Property Rights)] キラルピリジニウムリン酸アミド及びその利用 (2014)
  • Inventor(s): 西川泰弘、原脩
  • Industrial Property Rights Holder: 西川泰弘、原脩
  • Industrial Property Rights Type: 特許
  • Filing Date: 2014-11-10