パラジウム系キラル表面修飾触媒の新展開

• Project/Area Number: 20037058
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: University of Hyogo
• Principal Investigator: 杉村 高志 University of Hyogo, 大学院・物質理学研究科, 教授 (30187661)
• Project Period (FY): 2008 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥3,800,000 (Direct Cost: ¥3,800,000); Fiscal Year 2009: ¥1,900,000 (Direct Cost: ¥1,900,000); Fiscal Year 2008: ¥1,900,000 (Direct Cost: ¥1,900,000)
• Keywords: 不斉水素化 / 固体触媒 / キラル表面 / 分子認識 / パラジウム

Research Abstract

固体触媒のキラル修飾剤は触媒表面に十分な平衡定数を持って吸着し、基質の吸着を抑制、または促進し、基質の触媒上での反応を減速または加速する。すなわち修飾剤は触媒上の触媒と考えることができる。パラジウムをシンコニジン(CD)で修飾したCD修飾Pdは我々が改質Pd/Cを導入してから選択性が向上した。昨年の報告書ではこの触媒を用いた水中での反応を行い、Admix触媒を創出したことを報告している。Pd/Cの改質はフェニル桂皮酸以外の基質を用いた場合にも効果があり、その類縁体では不斉収率が92%に達した。βフェニル基上のメトキシ基の効果は大変大きい一方、αフェニル基上の置換基効果は明瞭ではなく、芳香環自体が高不斉収率に必須ではないことが判った。βアルコキシフェニル基質の高い立体選択性の理由は水素化速度の精密解析により明らかになった。基質の吸着の差が立体選択性に寄与すると、逆に触媒表面への吸着の強い基質は立体選択性が悪くなるはずである。吸着が非常に強い基質を用いてその機構を明らかにした。
シンコニジンの吸着はPd表面を被い水素化活性点を減少させるが、キラル修飾剤-基質相互作用は基本的に吸着を促進し、片方の反応を優位に進行させる必要があるため、加速効果になるはずである。CD-Pdでは加速効果が小さいため、CDと基質の吸着競争の効果が強くなり、これまで加速が観測されたことはない。シンコニジンの疑似エナンチオマーであるシンコニン(CN)とめ違いの検討の中で、不完全な修飾を行うと加速効果が実測できることを見いだした。
これまで市販のPd/Cを用いることにより触媒の汎用性を確保してきたが、さらなる改善と高立体区別機構の解析のためPd/Cの調製も行った。不斉収率は担持量が3%より大きくなると大きな変化が見られなかった。この結果は、Pd/TiO2の結果と大きく異なる。

Research Products

• [Journal Article] Enantioselective Hydrogenation of Olefins using CommerciallyAvailable Pd/C. Chiral Heterogeneous Catalyst Applicable for High-Throughput Screening (2010)
  • Author(s): Kim, T.Y., et al.
  • Journal Title: Topics Catal. 53 Pages: 116-122
  • Peer Reviewed
• [Journal Article] Substrate Adsorption on the Cinchonidine-Modified Pd/C during the Enantio-differe ntiating Hydrogenation as a Vital Stereocontrol Factor (2010)
  • Author(s): Misaki, T, et al.
  • Journal Title: J.Mol.Catal.Chem.A 313 Pages: 48-52
  • Peer Reviewed
• [Journal Article] Direct Asymmetric Aldol Reaction of 5H-Oxazol-4-ones with Aldehydes Catalyzed by Chiral Guanidines (2010)
  • Author(s): Misaki, T, et al.
  • Journal Title: J.Am.Chem.Soc. 132 Pages: 6286-6287
  • Peer Reviewed
• [Journal Article] Acceleration of Enantioselective Hydrogenation of Olefins over Pd/C by Cinchonidine as a Chiral Modifier. Comparison with Cinchonine (2010)
  • Author(s): Sugimura, T., Ogawa, H.
  • Journal Title: Chem.Lett. 39 Pages: 232-233
  • Peer Reviewed
• [Journal Article] キラル修飾パラジウム触媒 (2010)
  • Author(s): 御前智則・杉村高志
  • Journal Title: 月刊ファィンケミカル 39 Pages: 32-38
• [Journal Article] シンコニジン修飾Pd/C触媒 (2010)
  • Author(s): 杉村高志
  • Journal Title: Organic Squate 31 Pages: 2-4
• [Journal Article] Structural Requirements for Substrate in Highly Enantioselective Hydro genation over the Cinchonidine-Modified Pd/C. (2009)
  • Author(s): Sugimura, T., et al.
  • Journal Title: J.Catal. 262 Pages: 57-64
  • Peer Reviewed
• [Journal Article] Enantioselective Hydrogenation in Water over Chiral Modified Heterogeneous Catalyst Admixed with Organic Solvent. (2009)
  • Author(s): Sugimura, T. ; Kim, T.Y.
  • Journal Title: Catal.Lett. 130 Pages: 564-567
  • Peer Reviewed
• [Journal Article] A New Dialkyl Azodicarboxylate for the Mitsunobu Reaction (2009)
  • Author(s): K.Hagiya, et al.
  • Journal Title: Tetrahedron 65 Pages: 6109-6114
  • Peer Reviewed
• [Journal Article] Conditioning of palladium-on-carbon (Pd/C) for uniform cinchonidine modification to perform highly enantioselective hydrogenation (2009)
  • Author(s): T.Y.Kim, et al.
  • Journal Title: Catal. Lett. 1301 Pages: 279-284
  • Peer Reviewed
• [Journal Article] Enantioselective hydrogenation of (E)-a-phenylcinnamic acid over cinchonidine-modified Pd catalysts supported on TiO_2 and CeO_2 (2009)
  • Author(s): T.Kubota, et al.
  • Journal Title: Catal.Lett. 129 Pages: 387-393
  • Peer Reviewed
• [Journal Article] Structural Requirements for Substrate in Highly Enantioselective Hydrogenation over the Cinchonidine-Modified Pd/C (2009)
  • Author(s): Sugimura, T., et al.
  • Journal Title: J.Catal. 262 Pages: 57-64
  • Peer Reviewed
• [Journal Article] 4-(4-biphenylyl)-3-hydroxybutanoate via enantioselective hydrogenation using tartaric acid-modified nickel catalyst and direct recrystallization (2009)
  • Author(s): Sugimura, T., et al.
  • Journal Title: Tetrahedron : Asymmetry 20 Pages: 1877-1880
  • Peer Reviewed
• [Journal Article] Enantioselective Hydrogenation in Water over Chiral Modified Heterogeneous Catalyst Admixed with Organic Solvent (2009)
  • Author(s): T. Sugimura and T. Y. Kim
  • Journal Title: Catal. Lett (in press)
  • Peer Reviewed
• [Journal Article] Structural Requirements for Substrate in Highly Enantioselective Hydrogenation over the Cinchonidine-Modified Pd/C (2009)
  • Author(s): T. Sugimura, T. Uchida, J. Wat anabe, T. Kubota, Y. Okamoto, T. Misaki and T. Okuyama
  • Journal Title: J. Catal 262 Pages: 57-62
  • Peer Reviewed
• [Journal Article] Enantioselective hydrogenation of (E)-a-phenylcinnamic acid over cinchonidine-modified Pd catalysts supported on TiO2 and Ce02 (2009)
  • Author(s): T. Kubota, H. Kubota, T. Kubota, E. Moriyasu, T. Uchida, Y. Nitta, T. Sugimura and Y. Okamoto
  • Journal Title: Catal. Lett (in press)
  • Peer Reviewed
• [Presentation] 光学活性ジオキサニルカチオン中間体の生成と立体制御 (2010)
  • Author(s): 脇田三喜正
  • Organizer: 第5回分子情報ダイナミクス研究会
  • Place of Presentation: 吹田
  • Year and Date: 2010-03-31
• [Presentation] o-アルケニル安息香酸の不斉ラクトン化反応、第5回分子情報ダイナミクス研究会 (2010)
  • Author(s): 吉田泰志
  • Organizer: 第5回分子情報ダイナミクス研究会
  • Place of Presentation: 吹田
  • Year and Date: 2010-03-31
• [Presentation] シンコナ修飾によるPd水素化の加速効果 (2010)
  • Author(s): 杉村高志
  • Organizer: 第7回特定公開シンポジウム
  • Place of Presentation: 東工大
• [Presentation] シンコニジン水素化触媒のためのパラジウム炭素の調製 (2010)
  • Author(s): 小川裕之
  • Organizer: 第105触媒討論会
  • Place of Presentation: 京都
• [Presentation] パラジウム触媒不斉水素化に用いる修飾剤構造の必要条件 (2010)
  • Author(s): 佐野嘉恵
  • Organizer: 第90回日本化学会年会
  • Place of Presentation: 大阪
• [Presentation] 4-ジフェニルホスフィノ安息香酸を利用した光延反応の後処理法の開発 (2010)
  • Author(s): 村本夏子
  • Organizer: 第90回日本化学会年会
  • Place of Presentation: 大阪
• [Presentation] シンコナPd触媒を用いるチグリン酸水素化の立体区別機構解析 (2010)
  • Author(s): 戸祭総
  • Organizer: 第90回日本化学会年会
  • Place of Presentation: 大阪
• [Presentation] 適度に柔軟性を持たせたテンプレートによる閉環メタセシス反応 (2010)
  • Author(s): シディキ S.M.A.ハキム
  • Organizer: 第90回日本化学会年会
  • Place of Presentation: 大阪
• [Presentation] 光学活性ジオキソラニルカチオン中間体を経由する立体選択的酸化反応 (2010)
  • Author(s): 脇田三喜正
  • Organizer: 第90回日本化学会年会
  • Place of Presentation: 大阪
• [Presentation] 光学活性超原子価ヨウ素による位置および立体選択的δ-ラクトン生成反応 (2010)
  • Author(s): 吉田泰志
  • Organizer: 第90回日本化学会年会
  • Place of Presentation: 大阪
• [Presentation] ω-Functionahzed Decylmaltoside as a Co-Crystanization Detergent (2010)
  • Author(s): Tomonori Misaki
  • Organizer: The Annual Review Conference for the Fiscal Year of 2009
  • Place of Presentation: Kamigori
• [Presentation] A New Approach for Membrane Protein Crystallization (2010)
  • Author(s): Tomonori Misaki
  • Organizer: The Annual Review Conference for the Fiscal Year of 2009
  • Place of Presentation: Kamigori
• [Presentation] Pd/Cを用いるオレフィンの不斉水素化におけるシンコニジンとシンコニンの立体区別能力の違い (2009)
  • Author(s): 小川裕之
  • Organizer: 第2回触媒表面化学研究発表会
  • Place of Presentation: 大阪
  • Year and Date: 2009-10-09
• [Presentation] γ-ビフェニリルアセト酢酸エステルの酒石酸修飾ニッケル水素化と生成物の利用 (2009)
  • Author(s): 松田智博
  • Organizer: 第2回触媒表面化学研究発表会
  • Place of Presentation: 大阪
  • Year and Date: 2009-10-09
• [Presentation] 新規キラルグアニジン触媒を用いた5H-オキサゾール-4-オンのプロピオール酸エステルへのマイケル型付加反応の開発 (2009)
  • Author(s): 河野景
  • Organizer: モレキュラーキラリティー2009
  • Place of Presentation: 大阪
• [Presentation] 2, 4-ペンタンジオールをキラル架橋として用いる不斉メタセシス反応 (2009)
  • Author(s): シディキ・SMA・ハキム
  • Organizer: モレキュラーキラリティー
  • Place of Presentation: 大阪
• [Presentation] Adsorption on the Cinchonidine-Modified Pd/C during Enantio-differentiating Hydrogenation as a Vital Stereocontrol Facto (2009)
  • Author(s): Takashi Sugimura
  • Organizer: 特定領域協奏触媒第4回国際シンポジウム
  • Place of Presentation: 札幌
• [Presentation] Study on asymmetric metathesis reactioll using chiral tether (2009)
  • Author(s): Siddiki S.M.A.Hakim
  • Organizer: 21st International Symposium ; Synthesis in Organic Chemistry
  • Place of Presentation: Oxford
• [Presentation] Development of the Direct Asymmetric Aldol Reaction of 5H-Oxazol-4-ones Catalyzed by Novel Chiral Guanidine (2009)
  • Author(s): Tomonori Misaki
  • Organizer: 21st International Symposium ; Synthesis inOrganic Chemistry
  • Place of Presentation: Oxford
• [Presentation] Asymmetric intramolecular metathesis using chiral tether (2009)
  • Author(s): Siddiki S.M.A.Hakim
  • Organizer: 18th International Symposium on Olefin Metathesis and Related Chemistry
  • Place of Presentation: Leipzig
• [Presentation] Role of Water in Asymmetric Heterogeneous Catalysis UsingPd/C (2009)
  • Author(s): Tae Yeon Kim
  • Organizer: International Symposium on Relations between Homogeneous and Heterogeneous Catalysis
  • Place of Presentation: Stockholm
• [Presentation] CD修飾Pd触媒を用いるα、β飽和カルボン酸の不斉水素化反応:Amine添加なしの効果 (2009)
  • Author(s): 金台燕
  • Organizer: 第104回触媒討論会
  • Place of Presentation: 宮崎
• [Presentation] 超原子価ヨウ素化合物を用いたアルケンの酸化的環化反応の立体制御 (2009)
  • Author(s): 藤田守文
  • Organizer: 第19回基礎有機化学討論会
  • Place of Presentation: 桐生
• [Presentation] Palladium in Asymmetric Heterogeneous Catalysis (2009)
  • Author(s): T.Sugimura
  • Organizer: The 12th Japan-Korea Symposium on Catalysis
  • Place of Presentation: Akita
• [Presentation] Water in Asymmetric Hydrogenation with Cinchonidine-Modified Pd/C (2009)
  • Author(s): T.Y.Kim
  • Organizer: The 12th Japan-Korea Symposium on Catalysis
  • Place of Presentation: Akita
• [Presentation] New Chiral Modifiers for Enantioselective Hydrogenation of a,b-unsaturated acids using Palladium Catalyst (2009)
  • Author(s): T.Y.Kim
  • Organizer: The 12th Japan-Korea Symposium on Catalysis
  • Place of Presentation: Akita
• [Presentation] Recent Development in Chiral Modified Pd Catalyst (2009)
  • Author(s): Takashi Sugimura
  • Organizer: The 11th International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: Kyoto
• [Presentation] Chiral Modification of Palladium Catalyst Surface : Overview of Recent Progress in Asymmetric Synthesis (2009)
  • Author(s): Takashi Sugimura
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2009
  • Place of Presentation: Seoul
• [Presentation] Development of New Chiral Modifiers for Palladium Catalyst to Perform Enantioselective Hydrogenation (2009)
  • Author(s): Yoshie Sano
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2009
  • Place of Presentation: Seoul
• [Presentation] Preparation of (3R)-Methyl 4-(4-Biphenylyl)-3-hydroxybutanoate via Hydrogenation over Tartaric Acid-Modified Nickel (2009)
  • Author(s): Tomohiro Matsuda
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2009
  • Place of Presentation: Seoul
• [Presentation] Stereocontrollability of Cinchonidine vs. Cinchonine in the Enantioselective Hydrogenation of Olefins over Pd/C. (2009)
  • Author(s): Hiroyuki Ogawa
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2009
  • Place of Presentation: Seoul
• [Presentation] Conformational Multiplicity as a Stereocontrol Factor in the Chiral Tethered Reactions (2009)
  • Author(s): Siddiki S.M.A. Hakim
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2009
  • Place of Presentation: Seoul
• [Presentation] Asymmetric Michael Type AdditioIls of 5H-Oxazol-4-ones to Methyl Propiolates Catalyzed by Novel Chiral Guanidines (2009)
  • Author(s): Kei Kawano
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2009
  • Place of Presentation: Seoul
• [Presentation] Stereochemical Studies on the Mitsunobu Reaction Toward Asymmetric Catalysis (2009)
  • Author(s): Natsuko Muramoto
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2009
  • Place of Presentation: Seoul
• [Presentation] Water in Enantioselective Hydrogenation using Chiral Modified Palladium-on-Carbon (2009)
  • Author(s): Tae Yeon Kim
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2009
  • Place of Presentation: Seoul
• [Presentation] Stereoselective Oxidation of C=C Double Bond by Hiypervalent Iodine(III) (2009)
  • Author(s): Mikimasa Wakita
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2009
  • Place of Presentation: Seoul
• [Presentation] Direct Asymmetric Aldol Reactions of 5H-Oxazol-4-ones with Aldehydes Catalyzed by Novel Chiral Guanidines (2009)
  • Author(s): Tomonori Misaki
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2009
  • Place of Presentation: Seoul
• [Book] 物質科学の世界 (2010)
  • Author(s): 杉村高志(分著)
  • Total Pages: 198
  • Publisher: 共立出版
• [Book] Heterogeneous Enantioselective Hydrogenation on the Metal Surface Modifie d by Chiral Molecules. inHandbook of Asymmetric Heterogeneous Catalysis ; Ding, K.; Uozumi, Y. Eds (2008)
  • Author(s): T. Sugimura
  • Total Pages: 27
  • Publisher: Wiley-VCH : Verlag
• [Remarks]
  • URL: http://www.sci.u-hyogo.ac.jp/material/reaction2/index-j.html