Research on the design and synthesis of chiral NHC pincer ligands and their utility for asymmetric catalysis

• Project/Area Number: 23659014
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Chemical pharmacy
• Research Institution: Waseda University
• Principal Investigator: NAKADA Masahisa 早稲田大学, 理工学術院, 教授 (50198131)
• Project Period (FY): 2011 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000); Fiscal Year 2012: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2011: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
• Keywords: 有機化学 / 配位子 / ピンサー型配位子 / 不斉触媒 / 不斉触媒反応 / ＮＨＣ / 不斉配位子 / 触媒的不斉エポキシ化 / イミダゾリニウム塩

Research Abstract

A new chiral N-heterocyclic carbene (NHC) pincer-type ligand was synthesized. Its cationic platinum complex catalyzed an enantioselective cycloisomerization of a 1,5-ene-yne. A new preparation method of imidazolinium salts from the corresponding thioureas was developed. An asymmetric epoxidation catalyzed by a new iron (III) complex of a chiral C2-symmetric pincer-type ligand was discovered. Imidazolinium salts, precursors of chiral C2-symmetric NHC pincer-type ligands, were synthesized in high yields but were found to be unstable and difficult to convert to the corresponding transition metal complexes.

Research Products

• [Journal Article] A Non-Heme Iron (III) Complex with Porphyrin-Like Properties that Catalyzes Asymmetric Epoxidation (2012)
  • Author(s): Niwa, T.; Nakada, M
  • Journal Title: J. Am. Chem. Soc (Synfacts) Volume: 134 Issue: 33 Pages: 13538-13541
  • DOI: 10.1021/ja304219s
  • Peer Reviewed
• [Presentation] (2013)
  • Author(s): Niwa, T. ; Maeda, K. ; Nakada, M.
  • Organizer: The 4th Symposium on Chiral Science & Technology
  • Place of Presentation: 早稲田大学(東京)
• [Presentation] 鉄ポルフィリン様の反応性を示す鉄カルバゾール錯体を用いた触媒的不斉エポキシ化反応 (2012)
  • Author(s): 丹羽節、中田雅久
  • Organizer: 第45回酸化反応討論会
  • Place of Presentation: 名古屋市立大学(愛知)
• [Presentation] An Iron(III) Carbazole Complex with Porphyrin-Like Properties that Catayzes Asymmetric Epoxidation (2012)
  • Author(s): Niwa, T. ; Nakada, M.
  • Organizer: 59th Symposium on Organometallic Chemistry, Japan
  • Place of Presentation: 大阪大学(大阪)
• [Presentation] 複数配位子を有する鉄錯体を触媒としたアルケンの不斉エポキシ化反応の開発 (2012)
  • Author(s): 丹羽 節，中田雅久
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応大学、神奈川
• [Presentation] An Iron(III) Carbazole Complex with Porphyrin-Like Properties that Catayzes Asymmetric Epoxidation
  • Author(s): Niwa, T.; Nakada, M.（代表者）
  • Organizer: 59th Symposium on Organometallic Chemistry, Japan
  • Place of Presentation: 大阪大学（大阪）
• [Presentation] 鉄ポルフィリン様の反応性を示す鉄カルバゾール錯体を用いた触媒的不斉エポキシ化反応
  • Author(s): 丹羽節、中田雅久（代表者）
  • Organizer: 第４５回酸化反応討論会
  • Place of Presentation: 名古屋市立大学（愛知）
• [Presentation] A Non-Heme Iron(III) Complex with Porphyrin-Like Properties that Catalyzes Asymmetric Epoxidation
  • Author(s): Niwa, T.; Maeda, K.; Nakada, M.（代表者）
  • Organizer: The 4th Symposium on Chiral Science & Technology
  • Place of Presentation: 早稲田大学（東京）
• [Remarks]
  • URL: http://www.chem.waseda.ac.jp/nakada/