Reconstruction of Molecular Framework by C-C Bond Formation and Cleavage via Metalacycles
| Project/Area Number |
26288052
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Partial Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Nagasaki University |
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Principal Investigator |
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| Co-Investigator(Kenkyū-buntansha) |
重光 保博 長崎大学, 工学研究科, 准教授 (50432969)
小野寺 玄 長崎大学, 工学研究科, 助教 (90433698)
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| Project Period (FY) |
2014-04-01 – 2017-03-31
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| Project Status |
Completed (Fiscal Year 2016)
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| Budget Amount *help |
¥16,640,000 (Direct Cost: ¥12,800,000、Indirect Cost: ¥3,840,000)
Fiscal Year 2016: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2015: ¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000)
Fiscal Year 2014: ¥6,630,000 (Direct Cost: ¥5,100,000、Indirect Cost: ¥1,530,000)
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| Keywords | ニッケル / 銅 / 有機アルミニウム / 有機亜鉛 / アルキン / 二酸化炭素 / 共役ジエン / カーボネート / ジケテン / 多成分連結 / 炭素-炭素結合切断 / 合成化学 / 切断反応 / カップリング / 高効率 / フェニル酢酸 |
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| Outline of Final Research Achievements |
Although cyclic carbonates are utilized in fine chemicals and as monomers for polymerization in modern industrial synthesis, most synthetic utilities of 1,3-dioxolan-2-ones face difficulties due to the decarboxylation reaction. In this study, we have developed 4-methylene-1,3-dioxolan-2-one undergoes oxidative addition of Ni(0) catalyst in the presence of Me2Al(OMe) followed by a coupling reaction with alkynes to form unsaturated beta-ketocarboxylic acids with high regio- and stereoselectivities.
As an alternative development for CO2 fixation processes, we envisaged the three-component coupling reaction of terminal alkyne, trialkylboranes, and CO2 to yield alpha-substituted acrylic acids as a single product. Cu-catalyzed CO2 insertion reactions involving a dialkylvinylborane intermediate derived from alkynyltrialkylborate by a 1,2-alkyl group migration were carried out to afford α-alkylated acrylic acids with excellent regio- and stereoselectivities.
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Report
(4 results)
Research Products
(31 results)
