2013 Fiscal Year Final Research Report
Integrated Reaction using Unique Reactions
| Project Area | Organic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials |
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| Project/Area Number |
21106005
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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 | Kyoto University |
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Principal Investigator |
MATSUBARA Seijiro 京都大学, 工学(系)研究科(研究院), 教授 (90190496)
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| Project Period (FY) |
2009-07-23 – 2014-03-31
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| Keywords | 反応集積 / 有機亜鉛 / マイクロフロー / 環化 / タンデム反応 |
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| Research Abstract |
We had reported a novel tandem reaction using the gem-dizinc as a nucleophile to g-acyloxy-a,b-unsaturated ketone to afford a 1,3-diketone efficiently via three sequential steps. The reaction proceeds via three steps as shown in the scheme. DFT calculation showed that the activation energy for each steps decreases as the reaction proceeds. In addition, it also indicated that the whole reaction pathway was exothermic, and that two zinc atoms of bis(iodozincio)methane accelerated each step cooperatively as effective Lewis acids. Treatment of 1,6-dialkylhexa-1,5-diene-3,4-diones with bis(iodozincio)methane at -78 C for several hours gave cis-dialkenylcylopropane-1,2-diols which rearranged into the zinc alkoxides of cis-5,6-dialkylcyclohepta-3,7-diene-1,3-diol in good yields at room temperature as an one-pot reaction. When the reaction was performed using a microflow system, these two-step reactions can be performed in a few seconds at room temperature.
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