Advanced Eno I ate Formation and Reaction with Small Carbon Resources Catalyzed by Aminoorganometal Complexes

• Project/Area Number: 17065007
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Nagoya University
• Principal Investigator: SUSUMU Saito Nagoya University, 大学院・理学研究科, 准教授 (90273268)
• Project Period (FY): 2005 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥18,100,000 (Direct Cost: ¥18,100,000); Fiscal Year 2008: ¥5,100,000 (Direct Cost: ¥5,100,000); Fiscal Year 2007: ¥5,100,000 (Direct Cost: ¥5,100,000); Fiscal Year 2006: ¥5,300,000 (Direct Cost: ¥5,300,000); Fiscal Year 2005: ¥2,600,000 (Direct Cost: ¥2,600,000)
• Keywords: アミノ有機 / 金属錯体 / 水素結合 / 配位結合 / 環境負荷低減 / エノラート種の形成と反応 / 分子触媒 / アミノ有機金属触媒 / 炭素-炭素結合生成反応 / 酸-塩基相互作用 / ニトリル / アミド / 水和 / アミノ有機典型元素触媒 / 有機触媒 / プロリン / エナミン / シラノール / 形ある水 / 炭素-炭素結合生成 / エノール

Research Abstract

本研究では、斬新な分子構造をもっアミノ有機/(半)金属アルコキシド(MOR)系化合物を用いて、エノラート関連種を触媒的に発生させる新しい手法を見いだすとともに、その反応中間体としての合成的な有用性を、これまで実現が困難とされてきた反応系で展開させた。中性系分子触媒反応という新反応設計指針にその解決の糸口を見出した。すなわち、「水素(プロトン)移動に基づく触媒的なエノラート関連種の形成と反応の制御」に立脚し、高度な分子認識に基づく新しい分子触媒反応を多数開発し、廃棄物の排出を極力低減するための有機合成法へと拡張した。典型元素の活用に主眼をおきつつも、遷移金属の特徴を活かした分子触媒の探索にも視野を広げ研究を推進した。

Research Products

• [Journal Article] Cross-Coupling Reaction of Alcohols for Carboncarbon Bond Formation using Pincer-type-NHC/Palladium Catalyst. (2009)
  • Author(s): Kose, O.; Saito, S.
  • Journal Title: submitted for publication
  • Peer Reviewed
• [Journal Article] Importance of Open Structure of Non-metal Based Catalyst in Hydrogen Bond-promoted Methanolysis of Activated Amide: Structure Dynamics between Monomer and Dimer Enabling Recombinant Covalent, Dative, and Hydrogen Bonds. (2009)
  • Author(s): Oishi, S.; Yoshimoto, J.; Saito, S.
  • Journal Title: J. Am. Chem. Soc. 10 Pages: 1021-1021
  • Peer Reviewed
• [Journal Article] Importance of Open Structure of Non-metal Based Catalyst in Hydrogen Bond-promoted Methanolysis of Activated Amide : Structure Dynamics between Monomer and Dimer Enabling Recombinant Covalent, Dative, and Hydroaen Bonds (2009)
  • Author(s): Oishi, S. ; Yoshimoto, J. ; Saito, S.
  • Journal Title: J. Am. Chem. Soc. (submitted)
  • Peer Reviewed
• [Journal Article] Cross-Coupling Reaction of Alcohols for Carbon-carbon Bond Formation using Pincer-type-NHC/Palladium Catalyst (2009)
  • Author(s): Kose, O. ; Saito, S.
  • Journal Title: Chem. Commun. (submitted)
  • Peer Reviewed
• [Journal Article] Development of Organocatalysis Based on the Molecular Design of Pyrrolidine-Bronsted Acid Catalysts (2008)
  • Author(s): Saito, S.; Momiyama, M.; Yamamoto, H.
  • Journal Title: J. Synth. Org. Chem. Jpn. 66(8) Pages: 774-774
  • NAID: 10024278179
  • Peer Reviewed
• [Journal Article] Aqua Aminoorganoboron Catalyst: Engineering Single Water Molecule to Act as an Acid Catalyst in Nitro Aldol Reaction. (2008)
  • Author(s): Yoshimoto, J.; Sandoval, C.A.; Saito, S.
  • Journal Title: Chem. Lett. 37 Pages: 1294-1294
  • NAID: 10024398431
  • Peer Reviewed
• [Journal Article] RhI-catalyzed Hydration of Organonitriles Under Ambient Conditions. (2008)
  • Author(s): Goto, A.; Endo, K.; Saito, S.
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 3607-3607
  • Peer Reviewed
• [Journal Article] RhI-catalyzed Aldol-type Reaction of Organonitriles Under Mild Conditions. (2008)
  • Author(s): Goto, A.; Endo, K.; Ukai, Y.; Irle, S.; Saito, S.
  • Journal Title: Chem. Commun. Pages: 2212-2212
  • Peer Reviewed
• [Journal Article] Rh^I-catalyzed Aldol-type Reaction of Organonitriles Under Mild Conditions (2008)
  • Author(s): Goto, A. ; Endo, K. ; Ukai, Y. ; Irle, S. ; Saito, S.
  • Journal Title: Chem. Commun. 19 Pages: 2212-2214
  • Peer Reviewed
• [Journal Article] Rh^I-catalyzed Hydration of Organonitriles Under Ambient Conditions (2008)
  • Author(s): Goto, A. ; Endo, K. ; Saito, S.
  • Journal Title: Angew. Chem. Mt. Ed. 47 Pages: 3607-3609
  • Peer Reviewed
• [Journal Article] Aqua Aminoorganoboron Catalyst : Engineering Single Water Molecule to Act as an Acid Catalyst in Nitro Aldol Reaction (2008)
  • Author(s): Yoshimoto, J. ; Sandoval, C. A. ; Saito, S.
  • Journal Title: Chem. Lett. 37 Pages: 1294-1295
  • NAID: 10024398431
  • Peer Reviewed
• [Journal Article] Development of Organocatalysis Based on the Molecular Design of Pyrrolidine-Bronsted Acid Catalysts (2008)
  • Author(s): Saito, S. ; Momiyama, M. ; Yamamoto, H.
  • Journal Title: J. Synth. Org. Chem. Jpn. 66 Pages: 774-784
  • NAID: 10024278179
  • Peer Reviewed
• [Journal Article] ピロリジン-Brφnsted酸の分子設計に基づく有機分子触媒反応の開発 (2008)
  • Author(s): 斎藤 進, 椴山儀恵, 山本尚
  • Journal Title: 有機化学合成協会誌 (in press)
  • Peer Reviewed
• [Journal Article] Rh^I-catalyzed Aldol-type Reaction of Organonitriles Under Mild Conditions (2008)
  • Author(s): A. Goto, K. Endo, Y. Ukai, S. Irle, S. Saito
  • Journal Title: Chem. Commun. (in press)
  • Peer Reviewed
• [Journal Article] Rh^I-catalyzed Hydration of Organonitriles Under Ambient Conditions (2008)
  • Author(s): A. Goto, K. Endo, S. Saito
  • Journal Title: Angew. Chem. Int. Ed. (in press)
  • Peer Reviewed
• [Journal Article] 有機触媒を用いる酸-塩基相互作用の制御と有機アニオン種の形成に基づく不斉合成 (2007)
  • Author(s): 斎藤 進
  • Journal Title: 月刊ファインケミカル 36 Pages: 64-80
• [Journal Article] Me_3Al-Update (2007)
  • Author(s): S. Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis
  • Peer Reviewed
• [Journal Article] Et_3Al-Update (2007)
  • Author(s): S. Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis
  • Peer Reviewed
• [Journal Article] 有機触媒を用いる酸-塩基相互作用の制御と有機アニオン種の形成に基づく不斉合成 (2007)
  • Author(s): S.Saito
  • Journal Title: 月刊ファインケミカル (In press)
• [Journal Article] Me_3Al -Update- (2007)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis (In press)
• [Journal Article] Et_3Al -Update- (2007)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis (In press)
• [Journal Article] 東海から発信する産学官連携のトレンド (2006)
  • Author(s): 斎藤 進
  • Journal Title: 化学と工業 59(7) Pages: 784-784
• [Journal Article] Aluminum (2006)
  • Author(s): S.Saito
  • Journal Title: Comprehensive Organometallic Chemistry III 9 Pages: 245-296
• [Journal Article] Methylaluminum Bis(2,4,6-tri-t-butylphenoxide) -Update- (2006)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis
• [Journal Article] Methylaluminum Bis(2,6-di-t-butylphenoxide) -Update- (2006)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis
• [Journal Article] Methylaluminum Bis(2,6-di-t-butyl-4-methylphenoxide) -Update- (2006)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis
• [Journal Article] Methylaluminum Bis(2,6-di-phenylphenoxide) -Update- (2006)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis
• [Journal Article] Methylaluminum Bis(2,6-di-t-butyl-4-bromophenoxide) -Update- (2006)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis
• [Journal Article] Aluminum (2006)
  • Author(s): S.Saito
  • Journal Title: Comprehensive Organometallic Chemistry III (In press)
• [Journal Article] Me_3Al -Update- (2006)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis (In press)
• [Journal Article] Et_3Al -Update- (2006)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis (In press)
• [Journal Article] Methylaluminum Bis(2,4,6-tri-t-butylphenoxide) -Update- (2006)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis (In press)
• [Journal Article] Methylaluminum Bis(2,6-di-t-butylphenoxide) -Update- (2006)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis (In press)
• [Journal Article] Methylaluminum Bis(2,6-di-t-butyl-4-methylphenoxide) -Update- (2006)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis (In press)
• [Journal Article] Methylaluminum Bis(2,6-di-phenylphenoxide) -Update- (2006)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis (In press)
• [Journal Article] Methylaluminum Bis(2,6-di-t-butyl-4-bromophenoxide) -Update- (2006)
  • Author(s): S.Saito
  • Journal Title: Encyclopedia of Reagents for Organic Synthesis (In press)
• [Journal Article] 有機触媒を用いる環境調和型合成- (2005)
  • Author(s): S.Saito
  • Journal Title: 化学と工業 58(9) Pages: 1041-1042
• [Presentation] Open Structure of Non-metal-Based Catalyst in Neutral pH Catalysis: Structure Dynamics between Monomer and Dimer Enabling Recombinant Hydrogen, Dative, and Covalent Bonds, Second Japan-Singapore BilateralSymposiumonCatalysis (2009)
  • Author(s): S. Saito
  • Organizer: 第2回日本・シンガポール触媒シンポジウム
  • Place of Presentation: Kyoto University Clock Tower Centennial, Kyoto
• [Presentation] Open Structure of Non-metal-Based Catalyst in Neutral pH Catalysis : Structure Dynamics between Monomer and Dimer Enabling Recombinant Hydrogen, Dative, and Covalent Bonds (2009)
  • Author(s): S. Saito
  • Organizer: Second Japan-Singapore Bilateral Symposium on Catalysis
  • Place of Presentation: Kyoto University Clock Tower Centennial, Kyoto
• [Presentation] 強酸・強塩基触媒の化学から中性分子触媒化学への転換を目指して (2008)
  • Author(s): 斎藤進
  • Organizer: オルガノメタリックセミナーXXXIV「分子触媒化学の新パラダイム」
  • Place of Presentation: 九州大学国際ホール、博多
  • Year and Date: 2008-12-16
• [Presentation] [強酸・強塩基触媒の化学から中性分子触媒化学への転換を目指して」 (2008)
  • Author(s): 斎藤進
  • Organizer: オルガノメタリックセミナーXXXIV 「分子触媒化学の新パラダイム」
  • Place of Presentation: 九州大学国際ホテル、博多
  • Year and Date: 2008-12-16
• [Presentation] 野依パラダイムから地球環境に優しい化学物質生産へ一鍵となる物質:水素、水、二酸化炭素一 (2008)
  • Author(s): 斎藤進
  • Organizer: 日本技術士会東海支部冬季例会
  • Place of Presentation: 名古屋都市センター、名古屋
  • Year and Date: 2008-12-06
• [Presentation] 野依パラダイムから地球環境に優しい化学物質生産へ〜鍵となる物質 : 水素、水、二酸化炭素〜 (2008)
  • Author(s): 斎藤進
  • Organizer: 日本技術士会東海支部冬季例会
  • Place of Presentation: 名古屋都市センター、名古屋
  • Year and Date: 2008-12-06
• [Presentation] 強酸・強塩基触媒の化学から中性触媒化学への転換を目指して (2008)
  • Author(s): 斎藤進
  • Organizer: 岡山大学理学部講演会
  • Place of Presentation: 岡山大学
  • Year and Date: 2008-08-08
• [Presentation] Making Transition from Strong Acid or Base Catalysis to Neutral Catalysis (2008)
  • Author(s): S. Saito
  • Organizer: Annual Symposium on Global COE in Chemistry
  • Place of Presentation: Nagoya University
  • Year and Date: 2008-06-11
• [Presentation] 酸塩基交互配列型分子触媒の検証と応用 (2008)
  • Author(s): 大石俊輔、吉本純一、野依良治、斎藤 進
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 立教大学
  • Year and Date: 2008-03-26
• [Presentation] New Acid-base Cooperative Catalysis Using Aminoorganoboron Complexes (2008)
  • Author(s): S. Saito
  • Organizer: 7th IRTG Symposium for Miinster-Nagoya University
  • Place of Presentation: The University of Munster, Germany
• [Presentation] 「分子触媒を用いるアルコールの活性化と効率的有機合成への応用(Activation of Alcohols by Molecular Catalysts for Efficient Organic Synthesis) (2008)
  • Author(s): 小瀬修、安藤潤紀、s. Kai、野依良治、斎藤進
  • Organizer: 第55回有機金属化学討論会
  • Place of Presentation: 大阪府立大学、堺
• [Presentation] アミン系配位子/MOR型触媒を用いるエノラート種の生成と反応の新展開 (2008)
  • Author(s): 斎藤進
  • Organizer: 丸岡特定領域研究第5回公開講演会
  • Place of Presentation: 仙台国際センター、仙台
• [Presentation] 分子修飾型金属アルコキシドを用いる触媒的分子変換法の新展開 (2008)
  • Author(s): 斎藤進
  • Organizer: 第三回物質合成シンポジウム
  • Place of Presentation: 九州大学、博多
• [Presentation] 分子触媒を用いるアルコールの活性化と効率的有機合成への応用(Activation of Alcohols by Molecular Catalysts for Efficient Organic Synthesis) (2008)
  • Author(s): 小瀬修、安藤潤紀、S.Kai、野依良治、斎藤進
  • Organizer: 第55回有機金属化学討論会
  • Place of Presentation: 大阪府立大学、堺
• [Presentation] 分子修飾型金属アルコキシドを用いる触媒的分子変換法の新展開 (2008)
  • Author(s): 斎藤 進
  • Organizer: 第三回物質合成シンポジウム
  • Place of Presentation: 九州大学
• [Presentation] 「形ある水」を基盤とする触媒反応の開拓 (2007)
  • Author(s): 斎藤進
  • Organizer: 高砂香料工業特別講演会、高砂香料工業ファインケミカル研究所
  • Place of Presentation: 平塚
  • Year and Date: 2007-01-17
• [Presentation] Acid-base Alternating Molecular Catalysis-Design and Applications (2007)
  • Author(s): S. Saito
  • Organizer: 4th Annual Symposium on Japanese-German Frontiers of Science
  • Place of Presentation: International Shonan Village, Kanagawa.
• [Presentation] Design of Acid-base Catalysis for Organic Synthesis-Directed toward Direct Aldol Reaction of Organoamides- (2007)
  • Author(s): S. Saito
  • Organizer: 4th IRTG Symposium for Nagoya柚iinster University
  • Place of Presentation: The University of Miinster, Germany
• [Presentation] Design of Acid-base Catalysis for Organic Synthesis: Directed toward Direct Aldol Reaction of Organoamides (2007)
  • Author(s): S. Saito
  • Organizer: The 3rd IRTG Program for Nagoya-Munster Joint Seminar
  • Place of Presentation: Munster University, Germany
• [Presentation] Enolate formation and reaction promoted by molecular catalysts based on well-designed water molecule(s) (2006)
  • Author(s): Yoshimoto, J.; Goto, A.; Endo, K.; Oishi, S.; Nambo, M.; Noyori, R.; Saito, S.
  • Organizer: The 10th International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: Rihga Royal Hotel Kyoto, Japan
• [Presentation] 「形ある水」を 基盤とする精密分子触媒探索と有機合 成 (2006)
  • Author(s): 野依良治、斎藤進
  • Organizer: 物質合成研究機関連携事業大学問 連携・若手フォーラム
  • Place of Presentation: 関西セミナーハウス、京都
• [Book] 月刊ファインケミカル(有機触媒を用いる酸一塩基相互作用の制御と有機アニオン種の形成に基づく不斉合成) (2007)
  • Author(s): 斎藤進
• [Book] 有合化(山本尚先生, 玉尾皓平先生日本学士院賞を受賞, 65(5)) (2007)
  • Author(s): 斎藤進., 山口茂弘
  • Total Pages: 418
• [Book] 現代化学(山本 尚教授, 玉尾皓平教授に日本学士院賞-有機典型元素化合物の反応, 物性の開拓に貢献-) (2007)
  • Author(s): 斎藤進., 山口茂弘
  • Total Pages: 13
• [Book] in 'Encyclopedia of Reagents for Organic Synthesis, Et_3Al-Update - '(R. Paquette Ed.,) (2007)
  • Author(s): S. Saito
  • Publisher: John Wiley & Sons
  • URL: http://www.mrw.interscience.wiley.com/eros/articles/rt216/frame.html
• [Book] in 'Encyclopedia of Reagents for Organic Synthesis, Me3Al-Update-'(R. Paquette Ed.) (2007)
  • Author(s): S. Saito
  • Publisher: John Wiley & Sons
  • URL: http://www.mrw.interscience.wiley.com/eros/articles/rt265/frame.html
• [Book] in 'Comprehensive Organometallic Chemistry III; Aluminum(R.H. Carbtree, D.M.P. Mingos Eds) (2006)
  • Author(s): S. Saito
  • Publisher: Elsevier
• [Book] in 'Encyclopedia of Reagents for Organic Synthesis(R. Paquette Ed., Methylaluminum Bis(2, 4, 6-tri-t-butylphenoxide)-Update) (2006)
  • Author(s): S. Saito
  • Publisher: John Wiley & Sons
  • URL: http://www.mrw.interscience.wiley.com/eros/articles/rm136/frame.html.
• [Book] in 'Encyclopedia of Reagents for Organic Synthesis(R. Paquette Ed., Methylaluminum Bis(2, 6-di-t-butylphenoxide)-Update-) (2006)
  • Author(s): S. Saito
  • Publisher: John Wiley & Sons
  • URL: http://www.mrw.interscience.wiley.com/eros/articles/rm134/frame.html
• [Book] in 'Encyclopedia of Reagents for Organic Synthesis(R. Paquette Ed., Methylaluminum Bis(2, 6-di-t-butyl-4-methylphenoxide)-Update-) (2006)
  • Author(s): S. Saito
  • Publisher: John Wiley & Sons
  • URL: http://www.mrw.interscience.wiley.com/eros/articles/rm133/frame.html
• [Book] in 'Encyclopedia of Reagents for Organic Synthesis(R. Paquette Ed., Methylaluminum Bis(2, 6-di-phenylphenoxide)-Update -) (2006)
  • Author(s): S. Saito
  • Publisher: John Wiley & Sons
  • URL: http://www.mrw.interscience.wiley.com/eros/articles/rm135/frame.html
• [Book] in 'Encyclopedia of Reagents for Organic Synthesis(R. Paquette Ed., Methylaluminum Bis(2, 6-di-t-butyl-4-bromophenoxide)-Update-) (2006)
  • Author(s): S. Saito
  • Publisher: John Wiley & Sons
  • URL: http://www.mrw.interscience.wiley.com/eros/articles/rm132/frame.html
• [Book] 化学と工業(東海から発信する産学官連携のトレンド, 59(7)) (2006)
  • Author(s): 大島 康, 斎藤 進, 紫牟田 正則
  • Total Pages: 784
• [Book] 化学と工業(有機触媒を用いる環境調和型合成, 58(9)) (2005)
  • Author(s): 斎藤 進
• [Remarks] 高砂香料工業(株)と(株)カネカに譲渡売却済(平成21年2. 月16日通知)
• [Patent(Industrial Property Rights)] 炭酸エステルの製造方法 (2009)
  • Inventor(s): 野依良治、斎藤進、中寛史、角間香澄、Ya Du
  • Industrial Property Rights Holder: 国立大学法人名古屋大学
  • Filing Date: 2009-05-27
  • Acquisition Date: 2009-05-27
• [Patent(Industrial Property Rights)] 炭酸エステルの製造方法 (2009)
  • Inventor(s): 野依良治、斎藤進、中寛史、角間香澄、Ya Du
  • Industrial Property Rights Holder: 国立大学法人名古屋大学
  • Industrial Property Number: 2009-046589
  • Filing Date: 2009-02-27
• [Patent(Industrial Property Rights)] 液相でラクトンおよびカルボン酸エステルを水素化するアルコール類の製造方法 (2007)
  • Inventor(s): 野依良治、斎亜_進、前田博文、松本崇司、長崎出、井上健二
  • Industrial Property Rights Holder: 国立大学法人名古屋大学、(株)カネカ、高砂香料工業(株)
  • Filing Date: 2007-04-03
  • Acquisition Date: 2007-04-03
• [Patent(Industrial Property Rights)] 液相でラクトンおよびカルボン酸エステルを水素化するアルコール類の製造方法 (2007)
  • Inventor(s): 野依良治, 斎藤進, 前田博文, 井上健二, 長崎出, 松本崇司
  • Industrial Property Rights Holder: 国立大学法人名古屋大学, (株)カネカ, (株)高砂香料工業
  • Industrial Property Number: 2007-097618
  • Filing Date: 2007-04-03