Rhenium-Loaded TiO2

A Highly Versatile and Chemoselective Catalyst for the Hydrogenation of Carboxylic Acid Derivatives and the N-Methylation of Amines Using H2 and CO2

Takashi Toyao, S. M.A.H. Siddiki, Yoshitsugu Morita, Takashi Kamachi, Abeda S. Touchy, Wataru Onodera, Kenichi Kon, Shinya Furukawa, Hiroko Ariga, Kiyotaka Asakura, Kazunari Yoshizawa, Ken Ichi Shimizu

研究成果: ジャーナルへの寄稿記事

21 引用 (Scopus)

抄録

Herein, we report a heterogeneous TiO2-supported Re catalyst (Re/TiO2) that promotes various selective hydrogenation reactions, which includes the hydrogenation of esters to alcohols, the hydrogenation of amides to amines, and the N-methylation of amines, by using H2 and CO2. Initially, Re/TiO2 was evaluated in the context of the selective hydrogenation of 3-phenylpropionic acid methyl ester to afford 3-phenylpropanol (pH2 =5 MPa, =5 MPa, T=180 °C), which revealed a superior performance over other catalysts that we tested in this study. In contrast to other typical heterogeneous catalysts, hydrogenation reactions with Re/TiO2 did not produce dearomatized byproducts. DFT studies suggested that the high selectivity for the formation of alcohols in favor of the hydrogenation of aromatic rings is ascribed to the higher affinity of Re towards the COOCH3 group than to the benzene ring. Moreover, Re/TiO2 showed a wide substrate scope for the hydrogenation reaction (19 examples). Subsequently, this Re/TiO2 catalyst was applied to the hydrogenation of amides, the N-methylation of amines, and the N-alkylation of amines with carboxylic acids or esters.

元の言語英語
ページ(範囲)14848-14859
ページ数12
ジャーナルChemistry - A European Journal
23
発行部数59
DOI
出版物ステータス出版済み - 10 20 2017

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Rhenium
Methylation
Carboxylic Acids
Carboxylic acids
Hydrogenation
Amines
Derivatives
Catalysts
Esters
Amides
Alcohols
Alkylation
Benzene
Discrete Fourier transforms
Byproducts
Acids

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

これを引用

Rhenium-Loaded TiO2 : A Highly Versatile and Chemoselective Catalyst for the Hydrogenation of Carboxylic Acid Derivatives and the N-Methylation of Amines Using H2 and CO2. / Toyao, Takashi; Siddiki, S. M.A.H.; Morita, Yoshitsugu; Kamachi, Takashi; Touchy, Abeda S.; Onodera, Wataru; Kon, Kenichi; Furukawa, Shinya; Ariga, Hiroko; Asakura, Kiyotaka; Yoshizawa, Kazunari; Shimizu, Ken Ichi.

:: Chemistry - A European Journal, 巻 23, 番号 59, 20.10.2017, p. 14848-14859.

研究成果: ジャーナルへの寄稿記事

Toyao, T, Siddiki, SMAH, Morita, Y, Kamachi, T, Touchy, AS, Onodera, W, Kon, K, Furukawa, S, Ariga, H, Asakura, K, Yoshizawa, K & Shimizu, KI 2017, 'Rhenium-Loaded TiO2: A Highly Versatile and Chemoselective Catalyst for the Hydrogenation of Carboxylic Acid Derivatives and the N-Methylation of Amines Using H2 and CO2', Chemistry - A European Journal, 巻. 23, 番号 59, pp. 14848-14859. https://doi.org/10.1002/chem.201702801
Toyao, Takashi ; Siddiki, S. M.A.H. ; Morita, Yoshitsugu ; Kamachi, Takashi ; Touchy, Abeda S. ; Onodera, Wataru ; Kon, Kenichi ; Furukawa, Shinya ; Ariga, Hiroko ; Asakura, Kiyotaka ; Yoshizawa, Kazunari ; Shimizu, Ken Ichi. / Rhenium-Loaded TiO2 : A Highly Versatile and Chemoselective Catalyst for the Hydrogenation of Carboxylic Acid Derivatives and the N-Methylation of Amines Using H2 and CO2. :: Chemistry - A European Journal. 2017 ; 巻 23, 番号 59. pp. 14848-14859.
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abstract = "Herein, we report a heterogeneous TiO2-supported Re catalyst (Re/TiO2) that promotes various selective hydrogenation reactions, which includes the hydrogenation of esters to alcohols, the hydrogenation of amides to amines, and the N-methylation of amines, by using H2 and CO2. Initially, Re/TiO2 was evaluated in the context of the selective hydrogenation of 3-phenylpropionic acid methyl ester to afford 3-phenylpropanol (pH2 =5 MPa, =5 MPa, T=180 °C), which revealed a superior performance over other catalysts that we tested in this study. In contrast to other typical heterogeneous catalysts, hydrogenation reactions with Re/TiO2 did not produce dearomatized byproducts. DFT studies suggested that the high selectivity for the formation of alcohols in favor of the hydrogenation of aromatic rings is ascribed to the higher affinity of Re towards the COOCH3 group than to the benzene ring. Moreover, Re/TiO2 showed a wide substrate scope for the hydrogenation reaction (19 examples). Subsequently, this Re/TiO2 catalyst was applied to the hydrogenation of amides, the N-methylation of amines, and the N-alkylation of amines with carboxylic acids or esters.",
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T2 - A Highly Versatile and Chemoselective Catalyst for the Hydrogenation of Carboxylic Acid Derivatives and the N-Methylation of Amines Using H2 and CO2

AU - Toyao, Takashi

AU - Siddiki, S. M.A.H.

AU - Morita, Yoshitsugu

AU - Kamachi, Takashi

AU - Touchy, Abeda S.

AU - Onodera, Wataru

AU - Kon, Kenichi

AU - Furukawa, Shinya

AU - Ariga, Hiroko

AU - Asakura, Kiyotaka

AU - Yoshizawa, Kazunari

AU - Shimizu, Ken Ichi

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