Innovative Synthesis of Nitrogen-Containing Organic Compounds Using Diaminophpsphine Oxides and Multicatalytic Reaction Processes

• Project/Area Number: 18689001
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Chemical pharmacy
• Research Institution: Chiba University
• Principal Investigator: NEMOTO Tetsuhiro Chiba University, 大学院薬学研究院, 助教 (80361450)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥27,300,000 (Direct Cost: ¥21,000,000、Indirect Cost: ¥6,300,000); Fiscal Year 2008: ¥7,930,000 (Direct Cost: ¥6,100,000、Indirect Cost: ¥1,830,000); Fiscal Year 2007: ¥7,930,000 (Direct Cost: ¥6,100,000、Indirect Cost: ¥1,830,000); Fiscal Year 2006: ¥11,440,000 (Direct Cost: ¥8,800,000、Indirect Cost: ¥2,640,000)
• Keywords: 触媒的不斉合成 / ジアミノホスフィンオキシド / 連続触媒反応 / パラジウム / イリジウム / 2級ホスフィンオキシド / タングトリン / デカヒドロキノリン / アレン / 含室素化合物 / 多段階促進型触媒反応 / リン配位子 / 含窒素化合物

Research Abstract

私達の研究グループでは、窒素原子を分子骨格に有する化合物の合成法開発に焦点を絞り、基礎から応用研究まで総括的に検討を行った。独自に開発した触媒分子を応用、または組み合わせることにより、これまでの合成法では得る事が難しかった有機分子や、天然からの供給では分離の困難な化合物を効率的に得る手法を開拓した。

Research Products

• [Journal Article] Transition Metal-Catalyzed Asymmetric Reactions Using Chiral Diaminophosphine Oxides: DIAPHOXs. (2008)
  • Author(s): Tetsuhiro Nemoto
  • Journal Title: Chem. Pharm. Bull 56 Pages: 1213-1228
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Asymmetric Allylic Amination with Aromatic Amine Nucleophiles Using Chiral Diaminophosphine Oxides: DIAPHOXs (2008)
  • Author(s): Tetsuhiro Nemoto, Shinji Tamura, Tatsuro Sakamoto, and Yasumasa Hamada
  • Journal Title: Tetrahedron: Asymmetry 19 Pages: 1751-1759
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Asymmetric Allylic Alkylation of Cycloalkenyl Carbonates Using a Chiral Diaminophosphine Oxide: (S,RP)-Ph-DIAPHOX. (2008)
  • Author(s): Long Jin, Tetsuhiro Nemoto, Hiroshi Nakamura, and Yasumasa Hamada
  • Journal Title: Tetrahedron: Asymmetry 19 Pages: 1106-1113
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Asymmetric Allylic Alkylation of Cycloalkenyl Carbonates Using a Chiral Diaminophosphine Oxide : (S, R_P)-Ph-DIAPHOX (2008)
  • Author(s): Long Jin, Tetsuhiro Nemoto, Hiroshi Nakamura, and Yasumasa Hamada
  • Journal Title: Tetrahedron : Asymmetry 19 Pages: 1106-1113
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Asymmetric Allylic Amination with Aromatic Amine Nucleophiles Using Chiral Diaminophosphine Oxides : DIAPHOXs (2008)
  • Author(s): Tetsuhiro Nemoto, Shinji Tamura, Tatsuro Sakamoto, and Yasumasa Hamada
  • Journal Title: Tetrahedron : Asymmetry 19 Pages: 1751-1759
  • Peer Reviewed
• [Journal Article] Transition Metal-Catalyzed Asymmetric Reactions Using Chiral Diaminophosphine Oxides : DIAPHOXs (2008)
  • Author(s): Tetsuhiro Nemoto
  • Journal Title: Chem. Pharm. Bull 56 Pages: 1213-1228
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Asymmetric Allylic Amination of Morita-Baylis-Hillman Adduct Derivatives Using Chiral Diaminophosphine Oxides: DIAPHOXs. (2007)
  • Author(s): Tetsuhiro Nemoto, Takashi Fukuyama, Eri Yamamoto, Shinji Tamura, Tomoaki Fukuda, Takayoshi Matsumoto, Yuichi Akimoto, and Yasumasa Hamada.
  • Journal Title: Org. Lett. 9 Pages: 927-930
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Asymmtric Allylic Substitution Reactions Using P-Chirogenic Diaminophosphine Oxides: DIAPHOXs. (2007)
  • Author(s): Pd-Catalyzed Asymmtric Allylic Substitution Tetsuhiro Nemoto, and Yasumasa Hamada.
  • Journal Title: Chem. Rec. 7 Pages: 150-158
  • Peer Reviewed
• [Journal Article] Ir-Catalyzed Asymmetric Allylic Alkylation using Chiral Diaminophosphine Oxides: DIAPHOXs. Formal Enantioselective Synthesis of (-)-Paroxetine. (2007)
  • Author(s): Tetsuhiro Nemoto, Tatsuro Sakamoto, Takashi Fukuyama and Yasumasa Hamada
  • Journal Title: Tetrahedron Lett. 48 Pages: 4977-4981
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Enantioselective Synthesis of Quaternary α-Amino Acid Derivatives Using a Phenylalanine-Derived P-Chirogenic Diaminophosphine Oxide. (2007)
  • Author(s): Tetsuhiro Nemoto, Teisuke Harada, Takayoshi Matsumoto, and Yasumasa Hamada.
  • Journal Title: Tetrahedron Lett. 48 Pages: 6304-6307
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Asymmetric Allylic Alkylation of Cycloalkenyl Carbonates Using a Chiral Diaminophosphine Oxide: (S,R_P)-Ph-DIAPHOX. (2007)
  • Author(s): Tetsuhiro Nemoto, Tsukasa Hitomi, Hiroshi Nakamura, Long Jin, Keiichiro Hatano, and Yasumasa Hamada.
  • Journal Title: Tetrahedron: Asymmetry 18 Pages: 1844-1849
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Asymmtric Allylic Substitution Reactions Using P-Chirogenic Diaminophosphine Oxides: DIAPHOXs (2007)
  • Author(s): Tetsuhiro Nemoto, Yasumasa Hamada
  • Journal Title: The Chemical Records 7 Pages: 150-158
  • Peer Reviewed
• [Journal Article] Ir-Catalyzed Asymmetric Allylic Alkylation using Chiral Diaminophosphine Oxides: DIAPHOXs. Formal Enantioselective Synthesis (2007)
  • Author(s): Tetsuhiro Nemoto, Tatsuro Sakamoto, Takashi Fukuyama, Yasumasa Hamada
  • Journal Title: Tetrahedron Letters 48 Pages: 4977-4981
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Enantioselective Synthesis of Quaternary α-Amino Acid Derivatives Using a Phenylalanine-Derived P-Chirogenic Diaminophosphine Oxide (2007)
  • Author(s): Tetsuhiro Nemoto, Teisuke Harada, Takayoshi Matsumoto, Yasumasa Hamada
  • Journal Title: Tetrahedron Letters 48 Pages: 6304-6307
  • Peer Reviewed
• [Journal Article] Synthesis of a Novel P-Stereogenic Phenylphosphonamides and Application to Lewis Base- Catalyzed Asymmetric Allylation of Benzaldehyde (2007)
  • Author(s): Tetsuhiro Nemoto, Tsukasa Hitomi, Hiroshi Nakamura, Long Jin, Keiichiro Hatano, Yasumasa Hamada
  • Journal Title: Tetrahedron: Asymmetry 18 Pages: 1844-1849
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Asymmetric Allylic Amination of Morita-Baylis-Hillman Adduct Derivatives Using Chiral Diaminophosphine Oxides : DIAPHOXs (2007)
  • Author(s): Tetsuhiro Nemoto, Takashi Fukuyama, Eri Yamamoto, Shinji Tamura, Tomoaki Fukuda, Takayoshi Matsumoto, Yuichi akimoto, Yasumasa Hamada
  • Journal Title: Organic Letters 9 Pages: 927-930
• [Journal Article] Efficient Synthesis of 3-Substituted 2,3-Dihydroquinolin-4-one Using a One-Pot Sequential Multi-Catalytic Process: Pd-Catalyzed Allylic Amination-Thiazolium Salt-Catalyzed Stetter Reaction Cascade. (2006)
  • Author(s): Tetsuhiro Nemoto, Tomoaki Fukuda, and Yasumasa Hamada.
  • Journal Title: Tetrahedron Lett. 47 Pages: 4365-4368
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Asymmetric Allylic Alkylation with Nitromethane Using a Chiral Diaminophosphine Oxide: (S,R_P)-Ph-DIAPHOX. Enantioselective Synthesis of (R)-Preclamol and (R)-Baclofen (2006)
  • Author(s): Tetsuhiro Nemoto, Long Jin, Hiroshi Nakamura, and Yasumasa Hamada.
  • Journal Title: Tetrahedron. Lett. 47 Pages: 6577-6581
  • Peer Reviewed
• [Journal Article] Tetsuhiro Nemoto, Tatsurou Sakamoto, Takayoshi Matsumoto, and Yasumasa Hamada. (2006)
  • Author(s): Ir-Catalyzed Asymmetric Allylic Amination Using Chiral Diaminophosphine Oxides
  • Journal Title: Tetrahedron. Lett. 47 Pages: 8737-8740
  • Peer Reviewed
• [Journal Article] Efficient Synthesis of 3-Substituted 2,3-Dihydroquinolin-4-one Using a One-Pot Sequential Multi-Catalytic Process : Pd-Catalyzed Allylic Amination-Thiazolium Salt-Catalyzed Stetter Reaction Cascade (2006)
  • Author(s): Tetsuhiro Nemoto, Tomoaki Fukuda, Yasumasa Hamada
  • Journal Title: Tetrahedron Letters 47 Pages: 4365-4368
• [Journal Article] Pd-Catalyzed Asymmetric Allylic Alkylation with Nitromethane Using a Chiral Diaminophosphine Oxide : (S,R_p)-Ph-DIAPHOX. Enantioselective Synthesis of (R)-Preclamol and (R)-Baclofen (2006)
  • Author(s): Tetsuhiro Nemoto, Long Jin, Hiroshi Nakamura, Yasumasa Hamada
  • Journal Title: Tetrahedron Letters 47 Pages: 6577-6581
• [Journal Article] Ir-Catalyzed Asymmetric Allylic Amination Using Chiral Diaminophosphine Oxides (2006)
  • Author(s): Tetsuhiro Nemoto, Tatsurou Sakamoto, Takayoshi Matsumoto, Yasumasa Hamada
  • Journal Title: Tetrahedron Letters 47 Pages: 8737-6581
• [Presentation] デカヒドロキノリンtrans-195A及び2-epi体の不斉全合成研究 (2009)
  • Author(s): ○角河和未、福山尚、根本哲宏、濱田康正
  • Organizer: 日本薬学会129年会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-28
• [Presentation] Tangutorineの不斉全合成 (2009)
  • Author(s): 山本絵理、福山尚、Robert Franzen, 根本哲宏、濱田康正
  • Organizer: 日本薬学会129年会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-28
• [Presentation] キサンテン骨格を基盤とする新規キラル有機触媒の開発と応用 (2009)
  • Author(s): ○田村慎司、福山尚、小淵和通、根本哲宏、濱田康正
  • Organizer: 日本薬学会129年会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-28
• [Presentation] Pd-DIAPHOX触媒系を用いる光学活性アレン類の不斉合成 (2009)
  • Author(s): ○兼松睦、田村慎司、根本哲宏、濱田康正
  • Organizer: 日本薬学会129年会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-27
• [Presentation] 新規キラル2級ホスフィンオキシド配位子の開発と応用 (2009)
  • Author(s): 吉田真理子、金龍、○根本哲宏、濱田康正
  • Organizer: 日本薬学会129年会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-26
• [Presentation] Asymmetric Synthesis of Cyclic Aza-Morita-Baylis-Hillman Reaction Products Using Pd-DIAPHOX Catalyst System (2008)
  • Author(s): ○Tetsuhiro Nemoto, Takashi Fukuyama, Kazumi, Kakugawa, Yuko Maruyama, Yasumasa Hamada
  • Organizer: The 1st International Symposium on Process Chemistry
  • Place of Presentation: 京都
  • Year and Date: 2008-07-30
• [Presentation] Asymmetric Synthesis of Cyclic Aza-Morita-Baylis-Hiliman Reaction Products Usinn Pd-DIAPHOX Catalyst System (2008)
  • Author(s): Tetsuhiro Nemoto, Takashi Fukuyama, Kazumi, Kakugawa, Yuko Maruyama, Yasumasa Hamada
  • Organizer: The 1^<st> International Symposium on Process Chemistry
  • Place of Presentation: 京都
  • Year and Date: 2008-07-30
• [Presentation] Asymmetric Synthesis of Aza-Morita-Baylis-Hillman Reaction Products Using Pd-Chiral Diaminophosphine Oxide (DIAPHOX) Catalyst System (2008)
  • Author(s): ○Tetsuhiro Nemoto, Eri Yamamoto, Shinji Tamura, Takashi Fukuyama, Yasumasa Hamada
  • Organizer: 17th International Conference on Organic Synthesis
  • Place of Presentation: Daejeon, Korea
  • Year and Date: 2008-06-24
• [Presentation] Asymmetric Synthesis of Aza-Morita-Baylis-Hillman Reaction Products Using Pd-Chiral Diaminophosphine Oxide (DIAPHOX) Catalyst System (2008)
  • Author(s): Tetsuhiro Nemoto, Eri Yamamoto, Shinji Tamura, Takashi Fukuyama, Yasumasa Hamada
  • Organizer: 17^<th> International Conference on Organic Synthesis
  • Place of Presentation: Daejeon, Korea
  • Year and Date: 2008-06-24
• [Presentation] Pd-DIAPHOX触媒系を利用した芳香族アミンを求核剤とする不斉アリル位アミノ化反応 (2008)
  • Author(s): ○田村慎司、坂本達郎、根本哲宏、濱田康正
  • Organizer: 第55回有機合成化学協会関東支部シンポジウム
  • Place of Presentation: 野田
  • Year and Date: 2008-05-09
• [Presentation] ジアミノホスフィンオキシド類の配位子機能の開拓を基盤とする不斉遷移金属触媒反応の開発と応用 (2008)
  • Author(s): ○根本哲宏
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: 横浜
  • Year and Date: 2008-03-28
• [Presentation] Pd-ジアミノホスフィンオキシド触媒系を用いる含窒素キラル化合物の不斉合成 (2008)
  • Author(s): ○根本哲宏、濱田康正
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: 横浜
  • Year and Date: 2008-03-28
• [Presentation] Pd-ジアミノホスフィンオキシド触媒系を用いる含窒素キラル化合物の不斉合成 (2008)
  • Author(s): 根本哲宏、濱田康正
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: パシフィコ横浜
  • Year and Date: 2008-03-28
• [Presentation] ジアミノホスフィンオキシド類の配位子機能の開拓を基盤とする不斉遷移金属触媒反応の開発と応用 (2008)
  • Author(s): 根本哲宏
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: パシフィコ横浜
  • Year and Date: 2008-03-28
• [Presentation] Tangutorineの不斉全合成研究 (2008)
  • Author(s): ○山本絵理、福山尚、Robert Franzen、根本哲宏、濱田康正
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: 横浜
  • Year and Date: 2008-03-27
• [Presentation] Pd-DIAPHOX触媒系を用いる芳香族アミンを求核剤とする不斉アリル位アミノ化反応 (2008)
  • Author(s): ○田村慎司、坂本達郎、根本哲宏、濱田康正
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: 横浜
  • Year and Date: 2008-03-27
• [Presentation] Tangutorineの不斉全合成研究 (2008)
  • Author(s): 山本絵理、福山尚、Robert Franzen、根本哲宏、濱田康正
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: パシフィコ横浜
  • Year and Date: 2008-03-27
• [Presentation] Pd-DIAPHOX触媒系を用いる芳香族アミンを求核剤とする不斉アリル位アミノ化反応 (2008)
  • Author(s): 田村慎司、坂本達郎、根本哲宏、濱田康正
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: パシフィコ横浜
  • Year and Date: 2008-03-27
• [Presentation] デカヒドロキノリン骨格への立体選択的置換基導入法の検討 (2008)
  • Author(s): ○福山尚、角河和未、早崎留里子、根本哲宏、濱田康正
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: 横浜
  • Year and Date: 2008-03-26
• [Presentation] デカヒドロキノリン骨格への立体選択的置換基導入法の検討 (2008)
  • Author(s): 福山尚、角河和未、早崎留里子、根本哲宏、濱田康正
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: パシフィコ横浜
  • Year and Date: 2008-03-26
• [Presentation] アリル位アミノ化反応を鍵段階としたTangutorineの不斉全合成研究 (2007)
  • Author(s): ○福山尚、山本絵理、Robert Franzen、根本哲宏、濱田康正
  • Organizer: 第92回有機合成シンポジウム
  • Place of Presentation: 早稲田
  • Year and Date: 2007-11-08
• [Presentation] アリル位アミノ化反応を鍵段階としたTangutorineの不斉全合成研究 (2007)
  • Author(s): 福山尚、山本絵理、Robert Franzen、根本哲宏、濱田康正
  • Organizer: 第92回有機合成シンポジウム
  • Place of Presentation: 早稲田大学国際会議場
  • Year and Date: 2007-11-08
• [Presentation] Ir-DIAPHOX触媒系を用いる不斉アリル位置換反応 (2007)
  • Author(s): 坂本達郎、松本貴義、○根本哲宏、濱田康正
  • Organizer: 日本薬学会第127年会
  • Place of Presentation: 富山
  • Year and Date: 2007-03-29
• [Presentation] Pd-DIAPHOX触媒系を用いる4級アミノ酸の触媒的不斉合成 (2007)
  • Author(s): ○原田禎介、松本貴義、根本哲宏、濱田康正
  • Organizer: 日本薬学会第127年会
  • Place of Presentation: 富山
  • Year and Date: 2007-03-29
• [Presentation] 遷移金属.ジアミノホスフィンオキシド触媒系を用いる含窒素キラル化合物の触媒的不斉合成 (2006)
  • Author(s): ○根本哲宏、坂本達郎、福山尚、山本絵理、濱田康正
  • Organizer: 第32回反応と合成の進歩シンポジウム
  • Place of Presentation: 広島
  • Year and Date: 2006-12-05
• [Presentation] Catalytic Enantioselective Syntehsis of Cyclic Aza-Morita-Baylis-Hillman Adducts (2006)
  • Author(s): ○Tetsuhiro Nemoto, Takashi Fukuyama, Eri Yamamoto, Yasumasa Hamada
  • Organizer: 11th International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: 京都
  • Year and Date: 2006-11-14
• [Presentation] ジアミノホスフィンオキシド配位子(DIAPHOX)を用いる触媒的不斉反応の開発と応用 (2006)
  • Author(s): ○根本哲宏、福山尚、原田禎介、金龍、濱田康正
  • Organizer: 日本プロセス化学会2006サマーシンポジウム
  • Place of Presentation: 京都
  • Year and Date: 2006-07-21
• [Presentation] 光学活性ジアミノホスフィンオキシド類を用いる触媒的炭素-炭素、炭素.窒素結合形成反応の開発と生物活性化合物合成への応用 (2006)
  • Author(s): ○根本哲宏、福山尚、金龍、原田禎介、坂本達郎、中村浩、濱田康正
  • Organizer: 第89回有機合成シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2006-06-12
• [Remarks] 千葉大学大学院薬学研究院 薬化学研究室
  • URL: http://www.p.chiba-u.ac.jp/lab/yakka/index.html