| Budget Amount *help |
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2004: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2003: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2002: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2001: ¥1,000,000 (Direct Cost: ¥1,000,000)
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| Research Abstract |
We have found that the reduction of α-bromoamide could be achieved under mild conditions using Lewis acid and phosphine combination. Also, it has been already reported that the Reformatsky-type reaction could proceed when the aldehyde was reacted with the intermediate metal enolate, to give the desired β-hydroxyamide in good yield with high stereoselectivity. In this research, we would like to develop the synthetically useful reactions using this methodology.
At first, the Reformatsky reaction using α-bromoketones or thioesters, instead of α-bromoadmides, were investigated. As a result, the desired Reformatsky-type products were obtained in good yield with high stereoselectivity by using the combination of titanium tetrachloride and tri-o-tolylphosphine. Next, this reaction was applied to the other electrophile such as thioesters, acetals, and imines. The reaction with thioester have smoothly proceeded to give the reductive-Claisen condensate, and the Mannich-type reaction with imine was also found to give the corresponding adducts in good yield with high stereoselectivity. Moreover, other reductive reactions were also examined and we found the half-reduction of α-diketones, deoxygenation of sulfoxides and so on. Especially, the later was applied to the kinetic resolution of racemic phosphines to give optically active phosphines.
We found the several useful carbon-carbon bond forming reactions, reductive functional group interconversions using this combined reagent system. It was found that the combined reagent system was useful in the field of organic synthesis.
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