Development of acid-base bifunctional surfaces for efficient organocatalytic reactions

• Project/Area Number: 19760541
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Catalyst/Resource chemical process
• Research Institution: Tokyo Institute of Technology (2008); The University of Tokyo (2007)
• Principal Investigator: MOTOKURA Ken Tokyo Institute of Technology, 大学院・総合理工学研究科, 講師 (90444067)
• Project Period (FY): 2007 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥3,690,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥390,000); Fiscal Year 2008: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2007: ¥2,000,000 (Direct Cost: ¥2,000,000)
• Keywords: 触媒反応 / 不均一系触媒 / 触媒設計 / 酸・塩基 / 多機能触媒 / 有機合成

Research Abstract

固体酸シリカアルミナに3級および1級アミノ基をシランカップリング反応によって固定化した触媒が、種々の有機合成反応に極めて高い活性を示すことを見出した。これらの反応は均一系のアミンや、担体のシリカアルミナのみではほとんど進行しない。固定化触媒のアミノ基に由来する塩基点とSA表面の酸点の両方が機能して反応が進行するメカニズムを、固体NMRおよびFT-IRによって明らかにした。これらの知見を元に、より高活性を示す触媒の開発にも成功した。

Research Products

• [Journal Article] Acid-Base Bifunctional Catalysis of Silica-Alumina-Supported Organic Amines for Carbon-Carbon Bond-Forming Reactions (2008)
  • Author(s): Ken Motokura, Mitsuru Tomita, Mizuki Tada, and Yasuhiro Iwasawa
  • Journal Title: Chemistry-A European Journal 14 Pages: 4017-4027
  • NAID: 10019844489
  • Peer Reviewed
• [Journal Article] Acid-Base Bifunctional Catalytic Surfaces for Nucleophilic Addition Reactions (2008)
  • Author(s): Ken Motokura, Mizuki Tada, and Yasuhiro Iwasawa
  • Journal Title: Chemistry-An Asian Journal 3 Pages: 1230-1236
  • Peer Reviewed
• [Journal Article] Conceputual Integration of Homogeneous and Heterogeneous Catalyses (2008)
  • Author(s): Mizuki Tada, Ken Motokura, and Yasuhiro Iwasawa
  • Journal Title: Topics in Catalysis 48 Pages: 32-40
  • Peer Reviewed
• [Journal Article] Cooperative Catalysis of Primary and Tertiary Amines on Oxide Support Surface for One-Pot C-C Bond Forming Reactions (2008)
  • Author(s): Ken Motokura, Mizuki Tada, and Yasuhiro Iwasawa
  • Journal Title: Angewandte Chemie International Edition 47 Pages: 9230-9235
  • Peer Reviewed
• [Journal Article] Recyclable Indium Catalysts for Additions of 1,3-Dicarbonyl Compounds to Unactivated Alkynes Affected by Structure and Acid Strength of Solid Supports (2008)
  • Author(s): Kiyotomi Kaneda, Ken Motokura, Nobuaki Nakagiri, Tomoo Mizugaki, and Koichiro Jitsukawa
  • Journal Title: Green Chemistry 10 Pages: 1231-1234
  • Peer Reviewed
• [Journal Article] Photo-Induced Reversible Structural Transformation and Selective Oxidation Catalysis of Unsaturated Ru Complexes Supported on SiO2 (2008)
  • Author(s): Mizuki Tada, Yusaku Akatsuka, Yong Yang, Takehiko Sasaki, Mutsuo Kinoshita, Ken Motokura, and Yasuhiro Iwasawa
  • Journal Title: Angewandte Chemie International Edition 47 Pages: 9252-9255
  • Peer Reviewed
• [Journal Article] 無機酸化物表面の有機官能基化による高効率有機合成触媒の創出 (2008)
  • Author(s): 本倉健・岩澤康裕
  • Journal Title: 表面 46 Pages: 495-507
  • NAID: 40016329730
• [Journal Article] 固体表面における酸・塩基協同触媒作用を利用した高効率One-Pot炭素-炭素結合生成反応 -ニトロアルカン類の1,4-および1,2-付加反応- (2008)
  • Author(s): 本倉健・岩澤康裕
  • Journal Title: 触媒 50 Pages: 541-543
  • NAID: 10024280249
• [Journal Article] Acid-Base Bifunctional Catalytic Surfaces for Nucleophilic Addition Reactions (2008)
  • Author(s): Ken Motokura, Mizuki Tada, and Yasuhiro Iwasawa
  • Journal Title: Chemistry- An Asian Journal 3 Pages: 1230-1236
  • Peer Reviewed
• [Journal Article] Photo-Induced Reversible Structural Transformation and Selective Oxidation Catalysis of Unsaturated Ru Complexes Supported on SiO_2 (2008)
  • Author(s): Mizuki Tada, Yusaku Akatsuka, Yong Yang, Takehiko Sasaki, Mutsuo Kinoshita, Ken Motokura, and Yasuhiro Iwasawa
  • Journal Title: Angewandte Chemie International Edition 47 Pages: 9252-9255
  • Peer Reviewed
• [Journal Article] Acid-Base Bifunctional Catalysis of Silica-Alumina-Supported Organic A mines for Carbon-Carbon Bond-Forming Reactions (2008)
  • Author(s): Ken Motokura, Mitsuru Tomita, Mizuki Tada, and Yasuhiro Iwasawa
  • Journal Title: Chemistry - A European Journal 14 Pages: 4017-4027
  • Peer Reviewed
• [Journal Article] Creation of Acid-Base Bifunctional Catalysis for Efficient C-C Coupling Reactions by Amines Immobilization on SiO_2, Silica-Alumina, and Nano-H-ZSM-5 (2008)
  • Author(s): Ken Motokura, Nagabhatla Viswanadham, Gudimella Murali Dhar, and Yasuhiro Iwasawa
  • Journal Title: Catalysis Today (印刷中)(掲載確定)
  • Peer Reviewed
• [Journal Article] Heterogeneous Organic Base-Catalyzed Reactions Enhanced by Acid Supports (2007)
  • Author(s): Ken Motokura, Mizuki Tada, and Yasuhiro Iwasawa
  • Journal Title: Journal of the American Chemical Society 129 Pages: 9540-9541
  • Peer Reviewed
• [Journal Article] シリカアルミナ固定化有機アミンを酸・塩基両機能触媒として用いる不均一系炭素-炭素結合形成反応 (2007)
  • Author(s): 本倉健・岩澤康裕
  • Journal Title: 触媒 49 Pages: 423-425
  • NAID: 10019844489
• [Journal Article] Heterogeneous Orgainc Base-Catalyzed Reactions Enhanced by Acid Supports (2007)
  • Author(s): Ken Motokura, Mizuki Tada, and Yasuhiro Iwasawa
  • Journal Title: Journal of the American Chemical Society 129 Pages: 9540-9541
  • Peer Reviewed
• [Presentation] Multifunctional Heterogeneous Catalyses of Organic Amines Immobilized on Silica-Alumina Surfaces for Efficient Nucleophilic Addition Reactions (2008)
  • Author(s): Ken Motokura
  • Organizer: 4th International Symposium of BK21 Chemistry & Molecular Engineering Division and 16th International Symposium of SNU-UT-NTU Chemistry Departments(Invited)
  • Place of Presentation: Seoul, Korea
  • Year and Date: 2008-02-01
• [Presentation] Multifunctional Heterogeneous Catalyses or Organic Amines Immobilized on Silica-Alumina Surfaces for Efficient Nucleophilic Addition Reactions (2008)
  • Author(s): Ken Motokura
  • Organizer: 4^<th> International Symposium of BK21 Chemistry & Molecular Engineering Division and 16^<th> International Symposium of SNU-UT-NTU Chemistry Departments
  • Place of Presentation: Seolu, Korea
  • Year and Date: 2008-02-01
• [Presentation] 固体表面における酸・塩基協同触媒作用を利用した高効率One-Pot炭素-炭素結合生成反応, -ニトロアルカン類の1,4-および1,2-付加反応- (2008)
  • Author(s): 本倉健・岩澤康裕
  • Organizer: 第102回触媒討論会 討論会B
  • Place of Presentation: 名古屋
• [Presentation] Michael 反応のための有機塩基固定化固体酸触媒の開発 (2008)
  • Author(s): 富田満・本倉健・唯美津木・岩澤康裕
  • Organizer: 第102回触媒討論会 討論会A
  • Place of Presentation: 名古屋
• [Presentation] 1,4-Addition Reactions of Nitroalkanes and Thiols Catalyzed by Tunable Bifunctional Silica-Alumina Surfaces Immobilized with Tertiary Amines (2008)
  • Author(s): Ken Motokura, Satoka Tanaka, Mizuki Tada, and Yasuhiro Iwasawa
  • Organizer: 14th International Congress on Catalysis
  • Place of Presentation: Seoul, Korea
• [Presentation] Bifunctional Catalyses of Primary and Tertiary Amine-Immobilized Silica-Alumina for Nucleophilic Addition Reactions of Nitriles and Nitroalkanes (2008)
  • Author(s): Ken Motokura, Satoka Tanaka, Mitsuru Tomita, Mizuki Tada, and Yasuhiro Iwasawa
  • Organizer: International Symposium on Creation and Control of Advanced Selective Catalysis (a Pre-Symposium of 14th International Congress on Catalysis (ICC 14)) as the celebration of 50th anniversary of the Catalysis Society of Japan
  • Place of Presentation: Kyoto, Japan
• [Presentation] ニトロアルカンの付加反応におけるシリカアルミナ固定化1 級および3 級 アミンの新規協同触媒作用 (2008)
  • Author(s): 本倉健・田中里佳・富田満・唯美津木・岩澤康裕
  • Organizer: 日本化学会第88回春季年会
  • Place of Presentation: 東京
• [Presentation] 新規固定化有機アミン触媒の表面協同効果を利用した1,3-ジニトロプロパン類の高効率一段階合成 (2008)
  • Author(s): 本倉健・田中里佳・富田満・唯美津木・岩澤康裕
  • Organizer: 日本化学会第88回春季年会
  • Place of Presentation: 東京
• [Presentation] Bifunctional Catalyses of Primary and Tertiary Amine-Immobilized Silica-Alumina for Nucleophilic Addition Reactions of Nitriles and Nitroalkanes (2008)
  • Author(s): Ken Motokura, Satoka Tanaka, Mitsuru Tomita, Mizuki Tada, and Yasuhiro Iwasawa
  • Organizer: International Symposium on Creation and Control of Advanced Selective Catalysis (a Pre-Symposium of 14th International Congress on Catalysis (ICC 14)) as the celebration of 50^<th> anniversary of the Catalysis Society of Japan
  • Place of Presentation: Kyoto, Japan
• [Presentation] 1,4-Addition Reactions of Nitroalkanes and Thiols Catalyzed by Tunable Bifunctional Silica-Alumina Surfaces Immobilized with Tertiary Amines (2008)
  • Author(s): Ken Motokuran Satoka Tanaka, Mizuki Tada, and Yasuhiro Iwasawa
  • Organizer: 14^<th> International Congress on Catalysis
  • Place of Presentation: Seoul, Korea
• [Presentation] 固体表面における酸・塩基協同触媒作用を利用した高効率One-Pot炭素-炭素結合生成反応-ニトロアルカン類の1.4-および1, 2-付加反応- (2008)
  • Author(s): 本倉健・岩澤康裕
  • Organizer: 第102回触媒討論会討論会B
  • Place of Presentation: 名古屋
• [Presentation] Michael反応のための有機塩基固定化固体酸触媒の開発 (2008)
  • Author(s): 富田満・本倉健・唯美津木・岩澤康裕
  • Organizer: 第102回触媒討論会討論会A
  • Place of Presentation: 名古屋
• [Presentation] ニトロアルカンの付加反応におけるシリカアルミナ固定化1級および3級アミンの新規協同触媒作用 (2008)
  • Author(s): 本倉健・田中里佳・富田満・唯美津木・岩澤康裕
  • Organizer: 日本化学会第88回春季年会
  • Place of Presentation: 東京
• [Presentation] 新規固定化有機アミノ触媒の表面協同効果を利用した1,3-ジニトロプロパン類の高効率-段階合成 (2008)
  • Author(s): 本倉健・田中里佳・富田満・唯美津木
  • Organizer: 日本化学会第88回春季年会
  • Place of Presentation: 東京
• [Presentation] シリカアルミナ固定化有機アミンを酸・塩基両機能触媒として用いる不均一系炭素-炭素結合形成反応 (2007)
  • Author(s): 本倉 健・岩澤 康裕
  • Organizer: 第100回触媒討論会 討論会B
  • Place of Presentation: 札幌
• [Presentation] モンモリロナイトを固体酸触媒とする1,3-ジカルボニル化合物のオレフィンへの付加反応 (2007)
  • Author(s): 水垣共雄・本倉 健・中桐伸明・満留敬人・實川浩一郎・金田清臣
  • Organizer: 第100回触媒討論会
  • Place of Presentation: 札幌
• [Presentation] Organic Syntheses with Use of Silica-Alumina-Supported Tertiary and Primary Amines as Heterogeneous Bifunctional Catalysts (2007)
  • Author(s): Ken Motokura, Mizuki Tada, Satoka Tanaka, Mitsuru Tomita, and Yasuhiro Iwasawa
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2007(C&FC2007)
  • Place of Presentation: Singapore
• [Presentation] Highly Efficient 1,3-Dinitroalkane Synthesis with Use of Primary and Tertiary Amine Immobilized Solid Catalysts (2007)
  • Author(s): Ken Motokura, Mizuki Tada, Satoka Tanaka, Mitsuru Tomita, and Yasuhiro Iwasawa
  • Organizer: Singapore International Chemistry Conference 5(SICC5)
  • Place of Presentation: Singapore
• [Presentation] Silica-Alumina-Supported Amines as Heterogeneous Acid-Base Bifunctional Catalysts for Carbon-Carbon Bond-Forming Reactions (2007)
  • Author(s): Ken Motokura, Mizuki Tada, and Yasuhiro Iwasawa
  • Organizer: 12th Asian Chemical Congress(12ACC)
  • Place of Presentation: Kuala Lumpur, Malaysia
• [Presentation] Creation of Acid-Base Bifunctional Catalysis for Efficient Cyanation and Alkylation Reactions by Amines Immobilization on SiO2 and Nano-H-ZSM-5 (2007)
  • Author(s): Ken Motokura, Nagabhatla Viswanadham, Gudimella Murali Dhar, and Yasuhiro Iwasawa
  • Organizer: 18th National Symposium & Inso-US Seminar on Catalysis
  • Place of Presentation: India, Deradun
• [Presentation] Creation of Acid-Base Bifunctional Catalysis for Efficient Cyanation and Alkylation Reactions by Amines Immobilization on SiO_2 and Nano-H-ZSM-5 (2007)
  • Author(s): Ken Motokura, Nagabhatla Viswanadham, Gudimella Murali Dhar, and Yasuhiro Iwasawa
  • Organizer: 18^<th> National Symposium & Inso-US Seminar on Catalysis
  • Place of Presentation: India, Deradun
• [Presentation] Silica-Alumna-Supported Amines as heterogeneous Acid-Base Bifunctional Ctalysts for Carbon-Carbon Bond-Forming Reactions (2007)
  • Author(s): Ken Motokura, Mizuki Tada, and Yasuhiro Iwasawa
  • Organizer: 12^<th> Asian Chemical Congress (12ACC)
  • Place of Presentation: Kuala Lumpur, Malaysia
• [Presentation] Highly Efficient 1,3-Dinitroalkane Synthesis with Use of Primary and Tertiary Amine Immobilized Solid Catalysts (2007)
  • Author(s): Ken Motokura, Mizuki Tada, Satoka Tanaka, Mitsuru Tomita, and Yasuhiro Iwasawa
  • Organizer: Singapore Internatoinal Chemistry Conference 5 (SICC5)
  • Place of Presentation: Singapore
• [Presentation] Organic Syntheses with Use of Silica-Alumina-Supported Tertiary and Primary Amines as heterogeneous Bifunctional Catalysts (2007)
  • Author(s): Ken Motokura, Mizuki Tada, Satoka Tanaka, Mitsuru Tomita, and Yasuhiro Iwasawa
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2007 (C&FC2007)
  • Place of Presentation: Singapore
• [Presentation] シリカアルミナ固定化有機アミンを酸・塩基両機能触媒として用いる不均一系炭素-炭素結合形成反応 (2007)
  • Author(s): 本倉健・岩澤康裕
  • Organizer: 第100回触媒討論会
  • Place of Presentation: 札幌