2018 Fiscal Year Annual Research Report
ヘテロ環C(sp3)-H活性化に基づく新規触媒反応の開発
| Project/Area Number |
18J20833
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| Research Institution | Hokkaido University |
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Principal Investigator |
ZHANG DELIANG 北海道大学, 大学院総合化学院, 特別研究員(DC1)
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| Project Period (FY) |
2018-04-25 – 2021-03-31
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| Keywords | Iridium / Transfer hydrogenation / Heterogeneous catalyst / Dehydrogenation |
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| Outline of Annual Research Achievements |
The first project:Iridium-Catalyzed Alkene-Selective Transfer Hydrogenation with 1,4-Dioxane as Hydrogen Donor (in manuscript). Herein, an iridium-catalyzed transfer hydrogenation of alkenes using 1,4-dioxane as a hydrogen donor is described. The use of 1,2-bis(dicyclohexylphosphino)ethane (DCyPE), featuring bulky and highly electron-donating properties, exhibited high catalytic activity. This protocol allowed chemoselective transfer hydrogenation of alkenes over other potentially reducible functional groups such as carbonyl, nitro, cyano and imino groups in the same molecules.
The second project: reversible Dehydrogenation and Hydrogenation of N-Heterocycles with a Heterogeneous Bisphosphine-Ir Catalyst (on-going). Herein, we report a novel and efficient heterogeneous bisphosphine-Ir catalyst comprised of our original polystyrene-cross-linking bisphosphine PS-DPPBz and [IrCl(cod)]2 for the acceptorless dehydrogenation of N-heterocycles (Scheme 1). It should be noted that bisphoshine catalyst without ancillary ligand for acceptoless dehydrogantion reactions is rare. Moreover, the reverse process, namely, hydrogenation of unsaturated N-heterocycles proceeded with the same catalyst. Surprisingly, N-substituted heterocycles also underwent acceptorless dehydrogenations without hydrogen acceptors or oxidants, which indicates the reaction mechanism presumably distinct.
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| Current Status of Research Progress |
Current Status of Research Progress
1: Research has progressed more than it was originally planned.
Reason
As for the project of acceptorless dehydrogenation, I have expected the reaction can be performed in a large scale and produce large volume hydrogen gas. This may be valuable for the hydrogen fueling car. In the future, the reaction was expected to be performed for flow chemistry.
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| Strategy for Future Research Activity |
As for the project of acceptorless dehydrogenation. The reversible processes have been demonstrated by different N-heterocycles. Further investigation is on-going. Additionally, I will do the experiments to confirm the reaction mechanism. The reaction will be designed for flow chemistry and produce hydrogen gas in a large scale.
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