2014 Fiscal Year Final Research Report
Application of Unique Transition Metal Cluster Complexes for Catalytic Reactions
| Project Area | Molecule Activation Directed toward Straightforward Synthesis |
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| Project/Area Number |
22105010
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| Research Category |
Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Osaka University |
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Principal Investigator |
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| Project Period (FY) |
2010-04-01 – 2015-03-31
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| Keywords | クラスター / イリジウム２核錯体 / 触媒機能 / 不斉水素化反応 / 含窒素複素環化合物 / 光学活性環状アミン / 反応機構 / 塩素架橋複核錯体 |
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| Outline of Final Research Achievements |
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 was achieved by 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 investigated by time-course experiments, revealing that the addition of such the isoquinolinium chlorides clearly prevented the formation of catalytically inactive dinuclear trihydride complex, which was readily generated in the catalytic reduction of salt-free isoquinoline substrates. Based on mechanistic investigations, the function of the chloride anion of the isoquinolinium chlorides was elucidated, resulting in the new outer-sphere mechanism. The salt formation strategy was also applied for the asymmetric hydrogenation of pyridines.
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| Free Research Field |
有機金属化学
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