2013 Fiscal Year Final Research Report
Development of second generation of anionic tethered NHC ligand for achievement of reversal of enantioselectivity in catalytic asymmetric reaction
| Project/Area Number |
23550128
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Kansai University |
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Principal Investigator |
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| Project Period (FY) |
2011 – 2013
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| Keywords | 錯体・有機金属触媒 / 不斉触媒反応 / 含窒素複素環式カルベン / 銅触媒反応 / 共役付加反応 / 立体選択的反応 / リガンドデザイン / キラル配位子 |
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| Research Abstract |
Previously, we achieved the Cu-catalyzed asymmetric conjugate addition (ACA) reaction by the use of a CH2-bridged hydroxy-amide-functionalized azolium salt. Now, we designed and synthesized a (CH2)2-bridged hydroxy-amide-functionalized azolium salt. In comparison with the product which was obtained in the ACA reaction by Cu(OTf)2 combined with CH2-bridged azolium salt, the combination of Cu(OTf)2 with (CH2)2-bridged ligand led to the formation of the 1,4-adduct with opposite configuration. In addition, dual enantioselective control in the ACA reaction with the same ligand precursor was observed by changing the Cu precatalyst from Cu(OTf)2 to Cu(acac)2. Furthermore, a new ester-amide-functionalized azolium salt was also developed. It was found that the absolute configuration of the conjugate adduct in the ACA reaction using the ester-amide-functionalized azolium salt differs from that obtained in the ACA reaction using the hydroxy-amide-functionalized azolium salt.
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