Efficient direct asymmetric hydrogenation of N-heteroaromatic compounds to produce optically active cyclic amines
| Project/Area Number |
25620083
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| Research Category |
Grant-in-Aid for Challenging Exploratory Research
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| Allocation Type | Multi-year Fund |
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| Research Field |
Synthetic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
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| Project Period (FY) |
2013-04-01 – 2015-03-31
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| Project Status |
Completed (Fiscal Year 2014)
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| Budget Amount *help |
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2014: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2013: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
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| Keywords | 不斉水素化反応 / 複素芳香環化合物 / キノリン類 / キノキサリン類 / イソキノリン類 / ジヒドリドイリジウム錯体 / イリジウム二核錯体 / 外圏六員環遷移状態 / 不斉水素化 / イソキノリン / イリジウム / テトラヒドロイソキノリン / ヒドリド錯体 / ハロゲン架橋イリジウム二核錯体 / 光学活性２座ホスフィン配位子 / 複核イリジウム錯体 / ピペリジン / ピリジン塩酸塩 / 光学活性ピペリジン誘導体 / 含窒素複素環化合物 |
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| Outline of Final Research Achievements |
We found that asymmetric hydrogenation of 1- and 3-substituted and 1,3-disubstituted isoquinolinium chlorides using triply halide-bridged dinuclear iridium complexes [{Ir(H)(diphosphine)}2(μ-Cl)3]Cl (1) proceeded when we applied the strategy of the HCl salt formation of isoquinolines to afford the corresponding chiral 1,2,3,4-tetrahydroisoquinolines (THIQs) in high yield and excellent enantioselectivity after simple basic workup.
Effects of the salt formation were carefully evaluated based on controlled experiments including time-course experiments, 1H and 31P{1H} NMR studies, isolation, and characterization of several intermediates. Together with the function of the chloride anion of the isoquinolinium chlorides, we proposed a new outer-sphere mechanism including a coordination of the chloride anion of the substrates to an iridium dihydride species along with a hydrogen bond between the chloride ligand and the N-H proton of substrate salts.
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Report
(3 results)
Research Products
(9 results)
