Catalytic Method of Deuterium Gas Generation Using D_2O and Pd/C and Its Application to Synthesis of Deuterium-Labeled Compound
| Project/Area Number |
18590009
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Chemical pharmacy
|
|---|
| Research Institution | Gifu Pharmaceutical University |
|---|
Principal Investigator |
SAJIKI Hironao Gifu Pharmaceutical University, Pharmaceutical Sciences, Professor (50275096)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
MAEGAWA Tomohiro Gifu Pharmaceutical University, Pharmaceutical Sciences, Asociate Professor (40363890)
MONGUCHI Yasunari Gifu Pharmaceutical University, Pharmaceutical Sciences, Assistant Professor (40433205)
|
|---|
| Project Period (FY) |
2006 – 2007
|
| Project Status |
Completed (Fiscal Year 2007)
|
| Budget Amount *help |
¥4,020,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥420,000)
Fiscal Year 2007: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2006: ¥2,200,000 (Direct Cost: ¥2,200,000)
|
|---|
| Keywords | Organic Chemistry / Palladium / Deuteration / Deuterium Generation / Labeled by Stable-Isotope / 重水素ガス調製法 |
|---|
| Research Abstract |
The Pd/C-catalyzed H_2-D_2 exchange reaction between D_2O and H_2 and its application to the preparation of deuterium labeled compounds have been demonstrated. H_2 sealed in the reaction flask was efficiently converted into pure D_2, which can be used for the one-pot reductive deuteration of a variety of reducible functionalities. Furthermore, the chemoselective deuterogenation of olefins and acetylenes was accomplished by the addition of a trace amount of Ph_2S with retention of the various other reducible functionalities. A method of capturing the generated D_2 gas was also developed. The significant features of the H_2-D_2 exchange reaction are efficiency, inexpensiveness, environmental-friendly and convenience. Furthermore, a simple, mild, and regioselective H-D exchange reaction at the benzylic sites using the heterogeneous Pd/C as a catalyst without expensive D_2 gas was developed. The present method can afford the corresponding deuterium-labelled compounds with excellent deuterium efficiency. The use of 10% Pd/C in the presence of a small amount of hydrogen gas could achieve an efficient H-D exchange using the less expensive D-2O as the deuterium source at room temperature for 72 h. Furthermore, this reaction is dramatically accelerated under mild heating (50℃) conditions, resulting in shortening the reaction time and expanding the applicability of the substrates. The H-D exchange reaction could also be used for the deuteration of benzyl ethers, which were generally unstable under Pd/C-catalyzed hydrogenation conditions, with a high deuterium efficiency using Pd/C(en) instead of Pd/C. Furthermore, the use of THE and D_2O mixed (7:3) solvent successfully suppressed the hydrogenolysis of the corresponding benzyl ether. The present method would also be very useful for the simplification of complex ^1H NMR charts.
The general utility of these methodologies will make such simple techniques an attractive addition to the wide range of deuteration procedures.
|
Report
(3 results)
Research Products
(59 results)
-
-
-
-
-
[Journal Article] Facile and Convenient Method of Deuterium Gas Generation via Pd/C-catalyzed H_2?D_2 Exchange Reaction and Its Application to Synthesis of Deuterium-Labeled Compounds2008
Author(s)
Takanori, Kurita, Fumiyo, Aoki, Takuto, Mizumoto, Toshihide, Maejima, Hiroyoshi, Esaki, Tomohiro, Maegawa, Yasunari, Monguchi, Hironao, Sajiki
-
Journal Title
Chem. Eur. J 14
Pages: 3371-3379
Description
「研究成果報告書概要(欧文)」より
Related Report
-
[Journal Article] Pt/C-catalyzed efficient H-D exchange reaction of aromatic rings and its scope and limitations2008
Author(s)
Nobuhiro, Ito, Hiroyoshi, Esaki, Eikoh, Imamiya, Tsuneaki, Maesawa, Tomohiro, Maegawa, Hironao, Sajiki
-
Journal Title
Bull. Chem. Soc., Jpn 81
Pages: 278-286
Description
「研究成果報告書概要(欧文)」より
Related Report
-
-
-
-
-
-
-
-
[Journal Article] Efficient H-D Exchange Reaction of Alkyl-substituted Benzene Derivatives Using Pd/C-H_2-D_2O System2007
Author(s)
Hiroyoshi, Esaki, Fumiyo, Aoki, Miho, Umemura, Masatsugu, Kato, Tomohiro, Maegawa, Yasunari, Monguchi, Hironao, Sajiki
-
Journal Title
Chem. Eur,J 13
Pages: 4052-4063
Description
「研究成果報告書概要(欧文)」より
Related Report
-
-
[Journal Article] Method of Reaction of Labeling Deuterium Using Pd/C Catalyst2007
Author(s)
Hiroyoshi, Esaki, Takanori, Kurita, Yuta, Fujiwara, Tomohiro, Maegawa, Yasunari, Monguchi, Hironao, Sajiki
-
Journal Title
Journal of Synthetic Organic Chemistry 65
Pages: 1179-1190
Description
「研究成果報告書概要(欧文)」より
Related Report
-
[Journal Article] Efficient and Convenient Heterogeneous Palladium-Catalyzed Regioselective Deuteration at the Benzylic Position2007
Author(s)
Takanori, Kurita, Kazuyuki, Hattori, Saori, Seki, Takuto, Mizumoto, Fumiyo, Aoki, Yuki, Yamada, Kanoko, Ikawa, Tomohiro, Maegawa, Yasunari, Monguchi, Hironao, Sajiki
-
Journal Title
Chem. Eur. J 14
Pages: 664-673
Description
「研究成果報告書概要(欧文)」より
Related Report
-
-
-
-
-
-
-
-
-
-
[Journal Article] Mild and Efficient H-D Exchange of Alkanes Based on Activation Catalyzed by Heterogeneous Rhodium on Charcoal
Author(s)
Tomohiro, Maegawa, Yuta, Fujiwara, Yuya, Inagaki, Hiroyoshi, Esaki, Yasunari, Monguchi, Hironao, Sajiki
-
Journal Title
Angew. Chem. Mt. Ed (in press)
Description
「研究成果報告書概要(欧文)」より
Related Report
-
-
-
-
-
-
-
-
[Presentation] An Environmentally-Friendly and Catalytic Deuterium Gas Preparation Method Using Pd/C-D_2O-H_2 System2007
Author(s)
Takanori, Kurita, Fumiyo, Aoki, Takuto, Mizumoto, Hiroyoshi, Esaki, Tomohiro, Maegawa, Yasunari, Monguchi, Hironao, Sajiki
Organizer
3rd International Conference on Green and Sustainable Chemistry
Place of Presentation
Delft, Netherlands
Description
「研究成果報告書概要(欧文)」より
Related Report
-
[Presentation] Efficient Pd/C-Catalyzed H_2-D_2 Exchange Reaction in H_2-D_2O System2007
Author(s)
Takanori, Kurita, Fumiyo, Aoki, Takuto, Mizumoto, Hiroyoshi, Esaki, Tomohiro, Maegawa, Yasunari, Monguchi, Hironao, Sajiki
Organizer
1st Asian-Oceanian Conference on Green and Sustainable Chemistry/ 7th, GCS Symposium
Place of Presentation
Tokyo
Description
「研究成果報告書概要(欧文)」より
Related Report
-
[Presentation] Pd/C-catalyzed Efficient H-D Exchange Reaction of Alkanes2007
Author(s)
Yuta, Fujiwara, Yuya, Inagaki, Hiroyoshi, Esaki, Tomohiro, Maegawa, Yasunari, Monguchi, Hironao, Sajiki
Organizer
2007 Summer Symposium of the Japanese Society for Process Chemistry
Place of Presentation
Tokyo
Description
「研究成果報告書概要(欧文)」より
Related Report
-
-
[Presentation] Efficient H-D Exchange Reaction of Alkanes by Rh/C Catalyst2007
Author(s)
Yuta, Fujiwara, Yuya, Inagaki, Hiroyoshi, Esaki, Tomohiro, Maegawa, Yasunari, Monguchi, Hironao, Sajiki
Organizer
127th Annual Meeting of the Pharmaceutical Society of Japan
Place of Presentation
Toyama
Description
「研究成果報告書概要(欧文)」より
Related Report
-
[Presentation] Fastness Analysis Method of General Sulfonamid presented in a food by Labeling Deuterium Gemination Synthesize from H-D Exchange Reaction2007
Author(s)
Tomomi, Goto, Yuko, Ito, Teiji, Yamada, Tsutomu, Ohno, Sachiko, Yoshimi, Hisao, Oka, Hiroyosi, Esaki, Hironao, Sajiki, Kosaku, Hirota
Organizer
127th Annual Meeting of the Pharmaceutical Society of Japan
Place of Presentation
Toyama
Description
「研究成果報告書概要(欧文)」より
Related Report
-
-
-
-
-
-
-
-
[Presentation] Development of Pd/C-Catalyzed Deuterium Labeling Method and to the Tritiation2006
Author(s)
Tomohiro, Maegawa, Akira, Akashi, Kosaku, Hirota, Kenjiro, Tatematsu, Yukio, Mori, Hironao, Sajiki
Organizer
127th Annual Meeting of the Pharmaceutical Society of Japan
Place of Presentation
Osaka
Description
「研究成果報告書概要(欧文)」より
Related Report
-
-
-
-
-
-
-
-
-
-
-
