An Efficient Access to Chiral Compounds via Asymmetric Hydrogenation of Polar Functional Groups

• Project/Area Number: 21550096
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Kyushu University
• Principal Investigator: ITO Masato 九州大学, 先導物質化学研究所, 准教授 (20293037)
• 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: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2009: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: 触媒設計・反応 / 不斉合成反応 / 合成化学 / 触媒・科学プロセス / 水素 / 省エネルギー / 触媒・化学プロセス

Research Abstract

Novel molecular catalysts have been developed for the straightforward hydrogenation of a range of carboxylic acid derivatives under mild conditions. Modular design of chiral molecular catalysts could provide direct access to stereochemically well-defined moleculres, which might otherwise have required a detour to reach. Another important finding in this study is that the coexistence of inorganic base has led to dramatic improvement in their catalytic activity.

Research Products

• [Journal Article] Catalytic Hydrogenation of Carboxamides and Esters by Well-Defined Cp^* Ru Complexes Bearing a Protic Amine Ligand (2011)
  • Author(s): Masato Ito, Takashi Ootsuka, Ryo Watari Akira Shiibashi, Akio Himizu, Takao Ikariya
  • Journal Title: Journal of the American Chemical Society Volume: 113 Pages: 4240-4242
  • Peer Reviewed
• [Journal Article] Regioselective Lactonization of Unsymmetrical 1, 4-Diols : An Efficient Access to Lactone Lignans (2011)
  • Author(s): Masato Ito, Akira Shiibashi, Takao Ikariya
  • Journal Title: Chemical Communications Volume: 47 Pages: 2134-2136
  • Peer Reviewed
• [Journal Article] Regioselective Lactonization of Unsymmetrical 1,4-Diols ; An Efficient Access to Lactone Lignans (2011)
  • Author(s): Masato Ito, et al.
  • Journal Title: Chem.Commun. Volume: 47 Pages: 2134-2136
  • Peer Reviewed
• [Journal Article] Catalytic Hydrogenation of Carboxamides and Esters by Well-Defined Cp^*Ru Complexes Bearing a Protic Amine Ligand (2011)
  • Author(s): Masato Ito, et al.
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Pages: 4240-4242
  • Peer Reviewed
• [Journal Article] of 2-Aminoethanethiolato-bridged Dinuclear Ru(hmb) Complexes(hmb=η^6-hexamethylbenzene): Mechanistic Consideration on Transfer Hydrogenation with Bifunctional[ RuCl_2(hmb)]_2/2-Aminoethanethiol Catalyst System (2010)
  • Author(s): (3)Masato Ito, Akira Watanabe, Yuji Shibata, Takao Ikariya, Synthesis and Reactivity
  • Journal Title: Organometallics Volume: 29 Pages: 4584-4592
  • Peer Reviewed
• [Journal Article] Highly Enantioselective Hydrogenative Desymmetrization of Bicyclic Imides Leading to Multiply Functionalized Chiral Cyclic Compounds (2010)
  • Author(s): Masato Ito, Chika Kobayashi, Akio Himizu, Takao Ikariya
  • Journal Title: Journal of the American Chemical Society Volume: 132 Pages: 11414-11415
  • Peer Reviewed
• [Journal Article] Bifunctional Triflylamide-Tethered Cp. Rh and Cp. Ir Complexes : A New Entry for Asymmetric Hydrogenation Catalysts (2010)
  • Author(s): Masato Ito, Yoshinori Endo, Noriko Tejima, Takao Ikariya
  • Journal Title: Organometallics Volume: 29 Pages: 2397-2399
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of Protic Amine Tethered Rhodium(III) Peralkylcyclopentadienyl Complexes (2010)
  • Author(s): Masato Ito, Noriko Tejima, Masahiro Yamamura, Yoshinori Endo, Takao Ikariya
  • Journal Title: Organometallics Volume: 29 Pages: 1886-1889
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of Protic Amine Tethered Rh(III) Peralkylcyclopentadienyl Complexes (2010)
  • Author(s): Masato Ito, et al.
  • Journal Title: Organometallics Volume: 29 Pages: 1886-1889
  • Peer Reviewed
• [Journal Article] Bifunctional Triflylamide-Tethered Cp'Rh and Cp'Ir Complexes : A New Entry for Asymmetric Hydrogenation Catalysts (2010)
  • Author(s): Masato Ito, et al.
  • Journal Title: Organometallics Volume: 29 Pages: 2397-2399
  • Peer Reviewed
• [Journal Article] Highly Enantioselective Hydrogenative Desymmetrization of Bicyclic Imides Leading to Multiply Functionalized Chiral Cyclic Compounds (2010)
  • Author(s): Masato Ito, et al.
  • Journal Title: J.Am.Chem.Soc. Volume: 132 Pages: 11414-11415
  • Peer Reviewed
• [Journal Article] Synthesis and Reactivity of 2-Aminoethanethiolato-bridged Dinuclear Ru(hmb) Complexes (hmb=η^6-hexamethylbenzene) : Mechanistic Consideration on TransferHydrogenation with Bifunctional [RuCl_2(hmb)]_2/2-Aminoethanethiol Catalyst System (2010)
  • Author(s): Masato Ito, et al.
  • Journal Title: Organometallics Volume: 29 Pages: 4584-4592
  • Peer Reviewed
• [Journal Article] A Unique Functional Group Transformation of Planar Chiral Diolefinic Organonitrogen Cycles Utilizing PtCl_2(2,4,6-trimethylpyridine) Complexes (2010)
  • Author(s): Katsuhiko Tomooka, et al.
  • Journal Title: Organometallics Volume: 29 Pages: 6632-6635
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of Protic Amine Tethered Rh(III)Peralkylcyclopentadienyl Complexes (2010)
  • Author(s): M.Ito, et al.
  • Journal Title: Organometallics 29(掲載決定)
  • Peer Reviewed
• [Journal Article] (η^6-arene) Ru^<II>/Chiral SN Ligand : A Novel Bifunctional Catalyst System for Asymmetric Transfer Hydrogenation of Aromatic Ketones (2009)
  • Author(s): Masato Ito, Yuji Shibata, Akira Watanabe, Takao Ikariya
  • Journal Title: Synlett Pages: 1621-1626
  • Peer Reviewed
• [Journal Article] A Convenient Method for the Synthesis of Protic 2-(Tertiary phosphino)-1-amines and Their Cp* RuCl Complexes (2009)
  • Author(s): Masato Ito, Akihide Osaku, Chika Kobayashi, Akira Shiibashi, Takao Ikariya
  • Journal Title: Organometallics Volume: 28 Pages: 390-393
  • Peer Reviewed
• [Journal Article] Hydrogenation of N-Acylcarbamates and N-Acylsulfonamides Catalyzed by a Bifunctional[ Cp* Ru(PN)] Complex (2009)
  • Author(s): Masato Ito, Lee Wei Koo, Akio Himizu, Chika Kobayashi, Ayaka Sakaguchi, Takao Ikariya
  • Journal Title: Angewandte Chemie-International Edition Volume: 48 Pages: 1324-1327
  • Peer Reviewed
• [Journal Article] of Novel(η^1 :η^6-Aminoalkylarene) Ru^<II> Complexes (2009)
  • Author(s): Masato Ito, Hiroko Komatsu, Yoshinori Endo, Takao Ikariya, Synthesis and Structure
  • Journal Title: Chemistry Letters Volume: 38 Pages: 98-99
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of Novel(η^1:η^6-aminoalkylarene)Ru^<II> Complexes (2009)
  • Author(s): M.Ito, et al.
  • Journal Title: Chem.Lett. 38 Pages: 98-99
  • NAID: 10023990774
  • Peer Reviewed
• [Journal Article] Hydrogenation of N-Acylcarbamates and N-Acylsulfonamides Catalyzed by a Bifunctional Cp*Ru(PN)Complex (2009)
  • Author(s): M.Ito, et al.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 1324-1327
  • Peer Reviewed
• [Journal Article] A Convenient Method for the Synthesis of Protic 2-(Tertiaryphophino)1-amines and Their Cp*RuCl Complexes (2009)
  • Author(s): M.Ito, et al.
  • Journal Title: Organometallics 28 Pages: 390-393
  • Peer Reviewed
• [Journal Article] (η^6-arene)Ru^<II>/Chiral SN Ligand : A Novel Bifunctional Catalyst System for Asymmetric Transfer Hydrogenation of Aromatic Ketones (2009)
  • Author(s): M.Ito, et al.
  • Journal Title: Synlett(Cluster) Pages: 1621-1626
  • Peer Reviewed
• [Presentation] 新型キラル分子触媒の高度設計 (2011)
  • Author(s): 伊藤正人
  • Organizer: 有機合成秋季講演会
  • Place of Presentation: 鹿児島大学
  • Year and Date: 2011-12-08
• [Presentation] 新型キラル分子触媒の高度設計 (2011)
  • Author(s): 伊藤正人
  • Organizer: 有機合成秋季講演会
  • Place of Presentation: 鹿児島大学(招待講演)
  • Year and Date: 2011-12-08
• [Presentation] 新規トリフリルアミドテザー型Cp. Ru錯体の合成と反応性 (2011)
  • Author(s): 坂本直紀,遠藤慶徳,伊藤正人,碇屋隆雄
  • Organizer: 錯体化学会第61回討論会
  • Place of Presentation: 岡山理科大学
  • Year and Date: 2011-09-17
• [Presentation] プロティックアミンキレート配位子を有するCp^* Ru錯体を用いたN-アリールカルボン酸アミドの水素化反応 (2011)
  • Author(s): 亘理龍,大塚隆史,伊藤正人,碇屋隆雄
  • Organizer: 日本化学会第5回関東支部大会
  • Place of Presentation: 東京農工大学小金井キャンパス
  • Year and Date: 2011-08-30
• [Presentation] Ryo Watari, Takashi Ootsuka, Akira Shiibashi, Akio Himizu, Masato Ito, Hydrogenation of Esters and Carboxamides Promoted by Bifunctional Cp^* Ru Catalysts (2011)
  • Author(s): Ryo Watari, Takashi Ootsuka, Akira Shiibashi, Akio Himizu, Masato Ito, Takao Ikariya
  • Organizer: 16^<th> IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
  • Place of Presentation: Shanghai, China
  • Year and Date: 2011-07-24
• [Presentation] パラジウム触媒を用いる面不斉中員環アミド類のエナンチオ選択的合成 (2011)
  • Author(s): 伊藤正人, 他
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学横浜キャンパス
  • Year and Date: 2011-03-27
• [Presentation] Catalytic Hydrogenation of Carboxylic Acid Derivatives (2011)
  • Author(s): Masato Ito
  • Organizer: G-COE Symposium on Organic Chemistry in Fukuoka
  • Place of Presentation: Fukuoka, Japan
  • Year and Date: 2011-02-26
• [Presentation] Catalytic Hydrogenation of Carboxylic Acid Derivatives (2011)
  • Author(s): Masato Ito
  • Organizer: G-COE Symposium on Organic Chemistry in Fukuoka
  • Place of Presentation: 九州大学筑紫キャンパス
  • Year and Date: 2011-02-26
• [Presentation] Hydrogenation of Esters and Carboxamides Promoted by Bifunctional Cp^*Ru Catalysts (2011)
  • Author(s): 伊藤正人, 他
  • Organizer: The 16^<th> IUPAC International Symposium on OMCOS
  • Place of Presentation: Shanghai
• [Presentation] プロティックアミンキレート配位子を有するCp^*Ru錯体を用いたN-アリールカルボン酸アミドの水素化反応 (2011)
  • Author(s): 伊藤正人, 他
  • Organizer: 日本化学会第5回関東支部大会
  • Place of Presentation: 東京農工大学
• [Presentation] 新規トリフリルアミドテザー型Cp'Ru錯体の合成と反応性 (2011)
  • Author(s): 伊藤正人, 他
  • Organizer: 第61回錯体化学討論会
  • Place of Presentation: 岡山理科大学
• [Presentation] 面不斉9員環ジアリルアミド化合物の触媒的不斉合成 (2011)
  • Author(s): 伊藤正人, 他
  • Organizer: ナノマクロ物質デバイスシステム創製アライアンス成果報告会
  • Place of Presentation: ホテルメトロポリタン仙台
• [Presentation] デザイン型錯体分子触媒の開発 (2010)
  • Author(s): 伊藤正人
  • Organizer: 近未来新素材研究会第10回講演会
  • Place of Presentation: 九州大学
  • Year and Date: 2010-10-19
• [Presentation] デザイン型錯体分子触媒の開発 (2010)
  • Author(s): 伊藤正人
  • Organizer: 近未来新素材研究会第10回講演会
  • Place of Presentation: 九州大学筑紫キャンパス
  • Year and Date: 2010-10-19
• [Presentation] 代用元素利用を拝した省エネルギープロセスのための分子触媒設計 (2010)
  • Author(s): 伊藤正人
  • Organizer: ナノマクロ物質デバイスシステム創製アライアンスキックオフシンポジウム
  • Place of Presentation: 千里ライフサイエンスセンター
  • Year and Date: 2010-08-19
• [Presentation] 新規トリフリルアミドテザー型Cp'Ru錯体の合成と反応性 (2010)
  • Author(s): M.Ito, et al.
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス
  • Year and Date: 2010-03-29
• [Presentation] キラルCp*Ruアミン錯体によるラセミ体エステル類の動的速度論的分割を伴う不斉水素化反応 (2010)
  • Author(s): M.Ito, et al.
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス
  • Year and Date: 2010-03-26
• [Presentation] Molecular Catalysts for Straightforward Hydrogenation of Polarized Bonds (2010)
  • Author(s): Masato Ito
  • Organizer: Asian Core Program
  • Place of Presentation: National Taiwan University, Taiwan
  • Year and Date: 2010-01-23
• [Presentation] Molecular Catalysts for Straightforward Hydrogenation of Polarized Bonds (2010)
  • Author(s): Masato Ito
  • Organizer: Asian Core Program
  • Place of Presentation: National Taiwan Normal University, Taiwan
  • Year and Date: 2010-01-22
• [Presentation] Molecular Catalysts for Straightforward Hydrogenation of Polarized Bonds (2010)
  • Author(s): Masato Ito
  • Organizer: Asian Core Program
  • Place of Presentation: National Tsing Hua University, Taiwan
  • Year and Date: 2010-01-21
• [Presentation] 代用元素利用を拝した省エネルギープロセスのための分子触媒設計 (2010)
  • Author(s): 伊藤正人
  • Organizer: ナノマクロ物質デバイスシステム創製アライアンスG4分科会
  • Place of Presentation: 北海道大学創成科学研究棟
• [Presentation] Molecular Design of Bifunctional Cp* Ru Catalysts for Asymmetric Synthesis (2009)
  • Author(s): Masato Ito
  • Organizer: The 11^<th> International KYOTO conference on New Aspects of Organic Chemistry
  • Place of Presentation: Kyoto, Japan
  • Year and Date: 2009-11-12
• [Presentation] Molecular Design of Bifunctional Cp*Ru Catalysts for Asymmetric Synthesis (2009)
  • Author(s): M.Ito
  • Organizer: IKCOC11
  • Place of Presentation: Kyoto
  • Year and Date: 2009-11-12
• [Presentation] 機能性アミノテザーを有するRu, Rh, Ir錯体の構造とその触媒機能 (2009)
  • Author(s): 伊藤正人,遠藤慶徳,手島典子,碇屋隆雄
  • Organizer: 第104回触媒討論会
  • Place of Presentation: 宮崎大学工学部
  • Year and Date: 2009-09-30
• [Presentation] Cp^* Ru(PN)触媒を用いたトリオール類の高選択的ラクトン化反応 (2009)
  • Author(s): 伊藤正人,大澤康子,椎橋彬,碇屋隆雄
  • Organizer: 第104回触媒討論会
  • Place of Presentation: 宮崎大学工学部
  • Year and Date: 2009-09-30
• [Presentation] 機能性アミノテザーを有するRu, Rh, Ir錯体の構造をその触媒機能 (2009)
  • Author(s): M.Ito, et al.
  • Organizer: 第104回触媒討論会
  • Place of Presentation: 宮崎大学
  • Year and Date: 2009-09-30
• [Presentation] Cp*Ru(PN)触媒を用いたトリオール類の高選択的ラクトン化反応 (2009)
  • Author(s): M.Ito, et al.
  • Organizer: 第104回触媒討論会
  • Place of Presentation: 宮崎大学
  • Year and Date: 2009-09-30
• [Presentation] キラルCp*Ru(PN)触媒による環状アリルアルコールの不斉異性化反応 (2009)
  • Author(s): M.Ito, et al.
  • Organizer: 有機金属化学・有機合成化学学生ワークショップ
  • Place of Presentation: 九州大学筑紫地区
  • Year and Date: 2009-09-28
• [Presentation] SNキレート配位子を有する非対称二核錯体の生成機構 (2009)
  • Author(s): M.Ito, et al.
  • Organizer: 有機金属化学・有機合成化学学生ワークショップ
  • Place of Presentation: 九州大学筑紫地区
  • Year and Date: 2009-09-28
• [Presentation] 新規キラルCp*Ru(PN)錯体を用いた対称イミドの不斉水素化反応 (2009)
  • Author(s): M.Ito, et al.
  • Organizer: 有機金属化学・有機合成化学学生ワークショップ
  • Place of Presentation: 九州大学筑紫地区
  • Year and Date: 2009-09-28
• [Presentation] SNキレート配位子を有する非対称二核錯体の生成機構 (2009)
  • Author(s): 伊藤正人,渡邊章,柴田祐二,碇屋隆雄
  • Organizer: 錯体化学会第59回討論会
  • Place of Presentation: 長崎大学
  • Year and Date: 2009-09-26
• [Presentation] SNキレート配位子を有する非対称二核錯体の生成機構 (2009)
  • Author(s): M.Ito, et al.
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学
  • Year and Date: 2009-09-26
• [Presentation] Asymmetric Hydrogenation of Imides Catalyzed by Novel Cp^* Ru(PN) Complex (2009)
  • Author(s): Masato Ito, Akio Himizu, Chika Kobayashi, Takao Ikariya
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 同志社大学
  • Year and Date: 2009-09-11
• [Presentation] Asymmetric Hydrogenation of Imides Catalyzed by Novel Cp*Ru(PN)Complex (2009)
  • Author(s): M.Ito, et al.
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 同志社大学
  • Year and Date: 2009-09-11
• [Remarks] ホームページ
  • URL: http://www.researcherid.com/rid/G-3690-2010
• [Remarks]
  • URL: http://www.cm.kyushu-u.ac.jp/tomooka/mito/index.html
• [Remarks]
  • URL: http://www.cm.kyushu-u.ac.jp/tomooka/mito/index.html
• [Remarks]
  • URL: http://www.cm.kyushu-u.ac.jp/tomooka/mito/index.html
• [Patent(Industrial Property Rights)] Practical Method for Reducing Amides and Lactams (2010)
  • Inventor(s): 碇屋隆雄,伊藤正人,大塚隆史
  • Industrial Property Rights Holder: 東京工業大学・セントラル硝子
  • Acquisition Date: 2010-07-01
  • Overseas
• [Patent(Industrial Property Rights)] Practical Method for Reducing Esters and Lactones (2010)
  • Inventor(s): 碇屋隆雄,伊藤正人,椎橋彬,大塚隆史
  • Industrial Property Rights Holder: 東京工業大学・セントラル硝子
  • Acquisition Date: 2010-01-14
  • Overseas
• [Patent(Industrial Property Rights)] アミド類およびラクタム類の実用的な還元方法 (2010)
  • Inventor(s): 碇屋隆雄, 他
  • Industrial Property Rights Holder: 東工大・セントラル硝子
  • Filing Date: 2010-07-01
  • Overseas
• [Patent(Industrial Property Rights)] エステル類およびラクトン類の実用的な還元方法 (2010)
  • Inventor(s): 碇屋隆雄・伊藤正人・椎橋明・大塚隆史
  • Industrial Property Rights Holder: 東工大・セントラル硝子
  • Acquisition Date: 2010-01-14
  • Overseas