Synthetic studies on novel catalysts incorporating multi planar-chiral units

• Project/Area Number: 14350479
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Waseda University (2005); Meiji University (2002-2004)
• Principal Investigator: KANOMATA Nobuhiro Waseda University, Faculty of Science and Engineering, Professor (40221890)
• Project Period (FY): 2002 – 2005
• Project Status: Completed (Fiscal Year 2005)
• Budget Amount: ¥13,400,000 (Direct Cost: ¥13,400,000); Fiscal Year 2005: ¥900,000 (Direct Cost: ¥900,000); Fiscal Year 2004: ¥1,600,000 (Direct Cost: ¥1,600,000); Fiscal Year 2003: ¥1,600,000 (Direct Cost: ¥1,600,000); Fiscal Year 2002: ¥9,300,000 (Direct Cost: ¥9,300,000)
• Keywords: Stereocontrol of planar chirality / Cyclophane synthesis / Samarium iodide / Intramolecular pinacol coupling / Multi planar-chiral molecules / Phase transfer catalysts / Asymmetric alkylation / Crystallization-induced asymmetric transformation / 選択的合成・反応 / 不斉合成 / 酢酸銅 / 分子内アセチレンカップリング / 面下斉立体制御 / 面不斉分割

Research Abstract

This project aimed the new development of efficient synthetic methodologies to provide novel planar-chiral molecules and design/synthesis of multi planar-chiral molecules as novel phase transfer catalysts.
We have accomplished novel samarium-mediated intramolecular pinacol coupling for synthesis of a series of cyclophanediols in up to 64% yield which were transformed to planar-chiral[n] paracyclophanes(8-12). We have also developed stereocontrol of planar-chiral[11] paracyclophanes by using crystallization-induced asymmetric transformation. Synthesis of a series of[n] parapyridinophanes was also developed by the reaction of(vinylimino) phosphorane intermediates.
These planar-chiral pyridinophane and cyclophane molecules were transformed to multi planar-chiral ammonium salts and their asymmetric alkylation reactions were investigated as asymmetric phase transfer catalysis. Moderate enantioselectivity was observed with up to 75% ee for benzylation of a glycin derivative. We have thoroughly examined the catalytic activities of the pyridinophane and the cyclophane catalysts and the former showed the better enantioselectivities for asymmetric alkylation reactions.

Research Products

• [Journal Article] Synthesis of bridged nicotinates having[n](2,5)pyridinophane skeletons(n=8-14) (2006)
  • Author(s): 鹿又 宣弘, 他7名
  • Journal Title: Tetrahedron 62巻・17号 Pages: 4128-4138
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Synthesis of Bridged Nicotinates Having [n](2,5) Pyridinophane Skeletons(n=8-14) (2006)
  • Author(s): Nobuhiro Kanomata, Shinsuke Yamada, Takayuki Ohhama, Akira Fusano, Yoshiharu Ochiai, Jun Oikawa, Masahiro Yamaguchi, Fumio Sudo
  • Journal Title: Tetrahedron 62 Pages: 4128-4138
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Synthesis of bridged nicotinates having [n](2,5)pyridinophane skeletons (n=8-14) (2006)
  • Author(s): 鹿又宣弘, 山田慎介, 大浜隆之, 房野暁, 落合芳治, 他3名
  • Journal Title: Tetrahedron 62(印刷中)
• [Journal Article] Synthesis of Planar-Chiral Paracyclophanes via Samarium(II)-Catalyzed Intramolecular Pinacol Coupling (2005)
  • Author(s): 上田 剛・鹿又 宣弘・町田 肇
  • Journal Title: Organic Letters 7巻・12号 Pages: 2365-2368
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Synthesis of Planar-Chiral Paracyclophanes via Samarium(II)-Catalyzed Intramolecular Pinacol Coupling (2005)
  • Author(s): Tsuyoshi Ueda, Nobuhiro Kanomata, Hajime Machida
  • Journal Title: Organic Letters 7 Pages: 2365-2368
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Synthesis of Planar-Chiral Paracyclophanes via Samarium(II)-Catalyzed Intramolecular Pinacol Coupling (2005)
  • Author(s): 上田剛, 鹿又宣弘, 町田肇
  • Journal Title: Organic Letters 7 Pages: 2365-2368
• [Journal Article] 特異な構造を有する含窒素芳香族化合物の合成と機能に関する研究 (2003)
  • Author(s): 鹿又 宣弘
  • Journal Title: 有機合成化学協会誌 61巻・4号 Pages: 352-359
  • NAID: 10011905589
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] A simple method removing 2-oxazolidinone and 2-hydroxyethylamine auxiliaries in methoxide-carbonate systems for synthesis of planar-chiral nicotinate (2003)
  • Author(s): 鹿又 宣弘, 他3名
  • Journal Title: Tetrahedron Letters 44巻・18号 Pages: 3599-3603
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Adsorption-Induced Asymmetric Transformation of Planar-Chiral Pyridinophanes (2003)
  • Author(s): 鹿又 宣弘・及川 純
  • Journal Title: Tetrahedron Letters 61巻・18号 Pages: 3625-3628
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] N含有シクロファンの面不斉を立体制御する手法の開発 (2003)
  • Author(s): 鹿又 宣弘
  • Journal Title: ファインケミカル 32巻・19号 Pages: 5-13
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Studies on Syntheses and Functional Properties of Structurally Unique Nitrogen Aromatics (2003)
  • Author(s): Nobuhiro Kanomata
  • Journal Title: Journal of the Synthetic Organic Chemistry, Japan 61 Pages: 352-359
  • NAID: 10011905589
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] A Simple Method Removing 2-Oxazolidinone and 2-Hydroxyethylamine Auxiliaries in Methoxide-Carbonate Systems for Synthesis of Planar-Chiral Nicotinate (2003)
  • Author(s): Nobuhiro Kanomata, Satoshi Maruyama, Katsuhito Tomono, Shinnosuke Anada
  • Journal Title: Tetrahedron Letters 44 Pages: 3599-3603
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Adsorption-Induced Asymmetric Transformation of Planar-Chiral Pyridinophanes (2003)
  • Author(s): Nobuhiro Kanomata, Jun Oikawa
  • Journal Title: Tetrahedron Letters 44 Pages: 3625-3628
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Development of stereocontrol for the nitrogen-containing planar-chiral cyclophanes (2003)
  • Author(s): Nobuhiro Kanomata
  • Journal Title: Fine Chemical 32(19) Pages: 5-13
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] 鹿又宣弘: "特異な構造を有する含窒素芳香族化合物の合成と機能に関する研究"有機合成化学協会誌. 61巻・4号. 352-359 (2003)
• [Publications] 鹿又宣弘 他3名: "A Simple Method Removing 2-Oxazolidinone and 2-Hydroxyethylamine Auxiliaries in Methoxide-Carbonate Systems for Synthesis of Planar-Chiral Nicotinate"Tetrahedron Letters. 44巻・18号. 3599-3603 (2003)
• [Publications] 鹿又宣弘, 及川純: "Adsorption-Induced Asymmetric Transformation of Planar-Chiral Pyridinophanes"Tetrahedron Letters. 61巻・18号. 3625-3628 (2003)
• [Publications] 鹿又宣弘: "N含有シクロファンの面不斉を立体制御する手法の開発"ファインケミカル. 32巻・19号. 5-13 (2003)