Development of Metal-Encapsulating Silicone Gel Catalysts

• Project/Area Number: 21605009
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Element strategy
• Research Institution: Kyushu University
• Principal Investigator: MOTOYAMA Yukihiro 九州大学, 先導物質化学研究所, 准教授 (20283492)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2011: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2010: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2009: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
• Keywords: 合成化学 / 触媒 / 化学プロセス / 固定化触媒 / 環境対応 / 希少元素 / 触媒・化学プロセス

Research Abstract

In this work, we succeeded in immobilizing bipyridine and chiral bis(oxazoline) ligands bearing alkenyl moieties into the polysiloxane gels by hidrosilylation using polymethylhydrosiloxane and 1, 5-hexadiene. These ligand-encapsulating gels capture the Cu salts effectively to generate the catalytically active species in the gel. These metal-encapsulating silicone gels act as efficient recyclable catalysts for atom-transfer radical cyclization of alfa-halogenated acetoamides and asymmetric cyclopropanation of alkenes and diazoacetates without leaching of the metallic species.

Research Products

• [Journal Article] A Chiral Bis(oxazoline) Ligand Embedded into Polysiloxane Gel : Application to a Reusable Copper Catalyst for Asymmetric Cyclopropanation (2011)
  • Author(s): Motoyama, Y.; Nishikata, K.; Nagashima, H.
  • Journal Title: Chem. Asian J. Volume: 6 Pages: 78-82
  • Peer Reviewed
• [Journal Article] A Chiral Bis(oxazoline) Ligand Embedded into Polysiloxane Gel : Application to a Reusable Copper Catalyst for Asymmetric Cyclopropanation (2011)
  • Author(s): Motoyama, Y.; Nishikata, K.; Nagashima, H.
  • Journal Title: Chemistry An Asian Journal Volume: 6 Pages: 78-82
  • Peer Reviewed
• [Journal Article] Catalytic Atom-Transfer Radical Cyclization by Copper/Bipyridine Species Encapsulated in Polysiloxane Gel (2010)
  • Author(s): Motoyama, Y.; Kamo, K.; Yuasa, A.; Nagashima, H.
  • Journal Title: Chem. Commun. Volume: 46 Pages: 2256-2258
  • Peer Reviewed
• [Journal Article] Catalytic Atom-Transfer Radical Cyclization by Copper/Bipyridine Species Encapsulated in Polysiloxane Gel (2010)
  • Author(s): Motoyama, Y.; Kamo, K.; Yuasa, A.; Nagashima, H.
  • Journal Title: Chemical Communications 46 Pages: 2256-2258
  • Peer Reviewed
• [Presentation] A Chiral Bis(oxazoline) Ligand Embedded into Polysiloxane Gel : Application to a Reusable Copper Catalyst for Asymmetric Cyclopropanation (2011)
  • Author(s): Motoyama, Y.; Nishikata, T,; Nagashima, H.
  • Organizer: The Second International Symposium on Process Chemistry (ISPC 2011)
  • Place of Presentation: Kyoto
  • Year and Date: 2011-08-12
• [Presentation] A Chiral Bis(oxazoline) Ligand Embedded into Polysiloxane Gel : Application to a Reusable Copper Catalyst for Asymmetric Cyclopropanation (2011)
  • Author(s): Motoyama, Y.; Nishika ta, T.; Nagashima, H.
  • Organizer: The Second International Symposium on Process Chemistry
  • Place of Presentation: Kyoto
• [Presentation] ポリシロキサンゲル内包塩基複合型ロジウム触媒を用いたシリルカルボニル化反応 (2011)
  • Author(s): 鈴川喬之、本山幸弘、永島英夫
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川
• [Presentation] Catalytic Reactions in Metal-Encapsulated Polysiloxane Gels (2009)
  • Author(s): Motoyama, Y.; Yuasa, A.; Kamo, K.; Abe, M.; Kosako, Y.; Nagashima, H.
  • Organizer: GelSympo 2009(8th International Gel Symposium)
  • Place of Presentation: Oosaka
  • Year and Date: 2009-12-02
• [Presentation] Encapsulated Molecular Catalysts in Polysiloxane Gels : Copper/Bipyridine-Catalyzed Atom-Transfer Radical Cyclization (2009)
  • Author(s): Yuasa, A.; Kamo, K.; Abe, M.; Motoyama, Y.; Nagashima, H.
  • Organizer: The 11th International Kyoto Conference on New Aspects of Organic Chemistry(IKCOC-11)
  • Place of Presentation: Kyoto
  • Year and Date: 2009-11-12
• [Presentation] Catalysis in Polysiloxane Gel : Cu-Catalyzed Atom-Transfer Radical Cyclization of α-Halogenated Acetamide Derivatives (2009)
  • Author(s): Yuasa, A.; Kamo, K.; Abe, M.; Motoyama, Y.; Nagashima, H.
  • Organizer: 近畿化学会第56回有機金属化学討論会
  • Place of Presentation: 京都
  • Year and Date: 2009-09-10
• [Presentation] Catalytic Reactions in Metal-Encapsulated Polysiloxane Gels (2009)
  • Author(s): Motoyama, Y.; Yuasa, A.; Kamo, K.; Abe, M.; Kosako, Y.; Nagashima, H.
  • Organizer: GelSympo
  • Place of Presentation: Osaka
• [Presentation] Encapsulated MolecularCatalysts in Polysiloxane Gels : Copper/Bipyridine-Catalyzed Atom-Transfer Radical Cyclization (2009)
  • Author(s): Yuasa, A.; Kamo, K.; Motoyama, Y.; Nagashima, H.
  • Organizer: The 11th International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: Kyoto
• [Presentation] Catalysis in Polysiloxane Gel : Cu-Catalyzed Atom-Transfer Radical Cyclization ofα-Halogenated Acetamide Derivatives (2009)
  • Author(s): Yuasa, A.; Kamo, K.; Motoyama, Y.; Nagashima, H.
  • Organizer: 近畿化学会第56回有機金属化学討論会
  • Place of Presentation: 京都