Development of Novel Chiral Bifunctional Phase-Transfer Catalyst and Its Application to Environmentally Benign Asymmetric Reactions

• Project/Area Number: 22750093
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Kyoto University
• Principal Investigator: SHIRAKAWA Seiji 京都大学, 大学院・理学研究科, 准教授 (60459865)
• Project Period (FY): 2010 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2011: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2010: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
• Keywords: 不斉合成 / 有機触媒 / 相間移動触媒 / 環境調和型反応 / 触媒開発 / 原子効率 / 共役付加反応 / アミノ酸 / アミノ化反応 / フッ素化反応

Research Abstract

Asymmetric phase-transfer reaction is a powerful method for the efficient synthesis of biologically active compounds. Although many examples of chiral phase-transfer catalysts have been reported, truly efficient chiral phase-transfer catalyst is still limited. In this research, we have developed novel bifunctional phase-transfer catalysts for the asymmetric synthesis of useful compounds in drug development.

Research Products

• [Journal Article] Efficient Asymmetric Synthesis of a Bicyclic Amino Acid as a Core Structure of Telaprevir (2012)
  • Author(s): Seiji Shirakawa, 他3名
  • Journal Title: ChemCatChem Volume: 4(印刷中)(Web公開済) Issue: 7 Pages: 980-982
  • DOI: 10.1002/cctc.201200081
  • Peer Reviewed
• [Journal Article] The Direct Catalytic A symmetric Aldol Reaction ofα-Substituted Nitroacetates with Aqueous Formaldehyde under Base-FreeNeutral Phase-Transfer Conditions (2012)
  • Author(s): Shirakawa, S.; Ota, K.; Terao, S. J.; Maruoka, K.
  • Journal Title: Org. Biomol. Chem Volume: 10 Issue: 30 Pages: 5753-5753
  • DOI: 10.1039/c2ob07193b
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Synthesis of Axially Chiral o-Iodoanilides by Phase-Transfer Catalyzed Alkylations (2012)
  • Author(s): S. Shirakawa, K. Liu, and K. Maruoka
  • Journal Title: Journal of the American Chemical Society Volume: 134 Issue: 2 Pages: 916-919
  • DOI: 10.1021/ja211069f
  • Peer Reviewed
• [Journal Article] The Directl Catalystic Asymmetric Atdol Reaction of α-Substituted Nitroacetates with Aqueous Formal dehyde under Base-Free Neutral Phase-Transfer Conditions (2012)
  • Author(s): Seiji Shirakawa, 他3名
  • Journal Title: Org.Biomol.Chem. Volume: 10(印刷中)(Web公開済)
  • Peer Reviewed
• [Journal Article] Asymmetric Neutral Amination of Nitroolefins Catalyzed by Chiral Bifunctional Ammonium Salts in Water-Rich Biphasic Solvent (2011)
  • Author(s): L. Wang, S. Shirakawa, and K. Maruoka
  • Journal Title: Angewandt Chemie International Edition Volume: 50 Issue: 23 Pages: 5327-5330
  • DOI: 10.1002/anie.201101307
  • Peer Reviewed
• [Journal Article] Diastereo-and Enantioselective Conjugate Addition ofα-Substituted Nitroacetates to Maleimides under Base-Free Neutral Phase-Transfer Conditions (2011)
  • Author(s): Shirakawa, S.; Terao, S. J ; He, R.; Maruoka, K
  • Journal Title: Chem. Commun Volume: 47 Issue: 38 Pages: 10557-10559
  • DOI: 10.1039/c1cc14043d
  • Peer Reviewed
• [Journal Article] Phase-Transfer Catalyzed Asymmetric Synthesis of 1,1-Disubstituted Tetrahydroisoquinolines (2011)
  • Author(s): Seiji Shirakawa, 他4名
  • Journal Title: Adv.Synth.Catal. Volume: 353 Issue: 14-15 Pages: 2614-2618
  • DOI: 10.1002/adsc.201100269
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Synthesis of 1, 1-Disubstituted Tetrahydro-β-carbolines by Phase-Transfer Catalyzed Alkylations (2011)
  • Author(s): Shirakawa, S.; Liu, K.; Ito, H.; Maruoka, K.
  • Journal Title: Chem. Commun Volume: 47 Issue: 5 Pages: 1515-1517
  • DOI: 10.1039/c0cc04447d
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Synthesis of 1,1-Disubstituted Tetrahydro-β-carbo lines by Phase-Transfer Catalyzed Alkylations (2011)
  • Author(s): Seiji Shirakawa
  • Journal Title: Chem.Commun. Volume: 47 Pages: 1515-1517
  • Peer Reviewed
• [Journal Article] Chiral Bifunctional Phase Transfer Catalysts for Asymmetric Fluorination of β-Keto Esters (2010)
  • Author(s): Xisheng Wang
  • Journal Title: Chem.Commun. Volume: 46 Pages: 321-323
  • Peer Reviewed
• [Presentation] Base-Free Neutral Phase-Transfer Reaction System (2011)
  • Author(s): Seiji Shirakawa
  • Organizer: 2nd-ICCCS
  • Place of Presentation: The University of Queenslan (Australia)(招待講演)
  • Year and Date: 2011-11-01
• [Presentation] キラル相間移動触媒反応の新展開.塩基を用いない中性条件下での環境調和型キラル相間移動触媒反応. (2011)
  • Author(s): 白川誠司
  • Organizer: 社団法人新化学技術推進協会先端化学・材料技術部会講演会
  • Place of Presentation: 東京
  • Year and Date: 2011-06-30
• [Presentation] Asymmetric Phase-Transfer-Catalyzed Constructionof Quaetrnary Carbon Center in Chiral Cyclic Amines (2011)
  • Author(s): Liu, K.; Ito, H.; Shirakawa, S ; Maruoka, K.
  • Organizer: 5th Chem Comm International Symposium
  • Place of Presentation: Kyoto University, Kyoto, Japan
  • Year and Date: 2011-05-16
• [Presentation] Phase-Transfer Catalyzed Diastereoand Enantioselective Conjugate Additions ofα-Substituted Nitroacetates to Maleimides under Neutral Conditions (2011)
  • Author(s): Terao, S. J.; Shirakawa, S.; Maruoka, K
  • Organizer: 5th Chem Comm International Symposium
  • Place of Presentation: Kyoto University, Kyoto, Japan
  • Year and Date: 2011-05-16
• [Presentation] Asymmetric Neutral Amination of Nitroolefins Catalyzed by Chiral Bifunctional Ammonium Salt in Water-Rich Solvent (2011)
  • Author(s): Wang, L.; Shirakawa, S.; Maruoka, K.
  • Organizer: 5th Chem Comm International Symposium
  • Place of Presentation: Kyoto University, Kyoto, Japan
  • Year and Date: 2011-05-16
• [Presentation] Base-Free Neutral Phase-Transfer Reaction System (2011)
  • Author(s): Shirakawa, S.
  • Organizer: Second International Collaborative and Cooperative Chemistry Symposium
  • Place of Presentation: The University of Queensland,Queensland,Australia
• [Presentation] Phase-Transfer Catalyzed Asymmetric Synthesis of1, 1-Disubstituted Tetrahydro-β-carbolines and Tetrahydro isoquinolines (2011)
  • Author(s): Shirakawa, S.; Liu, K.; Ito, H.; Le, T. N.; Maruoka, K.
  • Organizer: The 7th International Symposium on Intergrated Synthesis(ISIS-7)
  • Place of Presentation: Kobe, Japan
• [Presentation] Practical Enantioselective Synthesis of Optically Active 1,1-Disubstituted Tetrahydro-β-carbolines by Phase-Transfer-Ctalyzed Alkylation (2010)
  • Author(s): Kun Liu
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2010-12-19
• [Presentation] Development of a Base-Free Chiral Phase-Transfer Reaction System (2010)
  • Author(s): Seiji Shirakawa
  • Organizer: The 6th International Symposium on Intergrated Synthesis (ISIS-6)
  • Place of Presentation: Maiko Villa Kobe, Kobe, Japan
  • Year and Date: 2010-10-24
• [Presentation] Development of a Base-Free Chiral Phase-Transfer Reaction System (2010)
  • Author(s): Shirakawa, S.; Wang, L.; He, R.; Maruoka, K.
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, Hawaii, USA
• [Presentation] Practical Enantioselective Synthesisof Optically Active 1, 1-Disubstituted Tetrahydro-β-carbolines by Phase-Transfer-Ctalyzed Alkylation (2010)
  • Author(s): Liu, K.; Shirakawa, S.; Maruoka, K.
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies(Pacifichem 2010)
  • Place of Presentation: Honolulu, Hawaii, USA
• [Presentation] Phase-Transfer Catalyzed Enantioselective Conjugate Additions ofα-Nitro Esters to Maleimides under Neutral Conditions (2010)
  • Author(s): Terao, S. J.; Shirakawa, S.; Maruoka, K.
  • Organizer: The 6th International Symposium on Intergrated Synthesis(ISIS-6)
  • Place of Presentation: Kobe, Japan
• [Presentation] Development of a Base-FreeChiral Phase-Transfer Reaction System (2010)
  • Author(s): Shirakawa, S.; Wang, L.; He, R.; Maruoka, K.
  • Organizer: The 6th International Symposium on Intergrated Synthesis(ISIS-6)
  • Place of Presentation: Kobe, Japan
• [Book] "Phase-Transfer Catalysis : Non-Natural-Product-Derived PTC" In Science of Synthesis : Asymmetric Organocatalysis 2 (2012)
  • Author(s): Shirakawa, S.; Maruoka, K.
  • Publisher: Georg Thieme Verlag
• [Book] "Asymmetricα-Functionalization of Carbonyl Compounds and Alkylation of Enolates" In Science of Synthesis : Water in Organic Synthesis (2012)
  • Author(s): Shirakawa, S.; Maruoka, K.
  • Publisher: Georg Thieme Verlag
• [Book] Science of Synthesis : Asymmetric Organocatalysis 2 (2012)
  • Author(s): Seiji Shirakawa, Keiji Maruoka
  • Publisher: Georg Thieme Verlag KG
• [Book] "Asymmetric Phase-Transfer and Ion Pair Catalysis" In CatalyticAsymmetric Synthesis (2010)
  • Author(s): Shirakawa, S.; Maruoka, K.
  • Publisher: John Wiley & Sons
• [Book] Catalytic Asymmetric Synthesis, 3rd ed. (2010)
  • Author(s): Seiji Shirakawa
  • Publisher: John Wiley & Sons
• [Remarks]
  • URL: http://kuchem.kyoto-u.ac.jp/yugo/orgcat/index.html
• [Remarks]
  • URL: http://kuchem.kyoto-u.ac.jp/yugo/orgcat/index.html