| Budget Amount *help |
¥37,180,000 (Direct Cost: ¥28,600,000、Indirect Cost: ¥8,580,000)
Fiscal Year 2013: ¥7,280,000 (Direct Cost: ¥5,600,000、Indirect Cost: ¥1,680,000)
Fiscal Year 2012: ¥7,280,000 (Direct Cost: ¥5,600,000、Indirect Cost: ¥1,680,000)
Fiscal Year 2011: ¥7,280,000 (Direct Cost: ¥5,600,000、Indirect Cost: ¥1,680,000)
Fiscal Year 2010: ¥7,280,000 (Direct Cost: ¥5,600,000、Indirect Cost: ¥1,680,000)
Fiscal Year 2009: ¥8,060,000 (Direct Cost: ¥6,200,000、Indirect Cost: ¥1,860,000)
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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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