| Budget Amount *help |
¥17,400,000 (Direct Cost: ¥15,600,000、Indirect Cost: ¥1,800,000)
Fiscal Year 2007: ¥7,800,000 (Direct Cost: ¥6,000,000、Indirect Cost: ¥1,800,000)
Fiscal Year 2006: ¥9,600,000 (Direct Cost: ¥9,600,000)
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| Research Abstract |
We demonstrated that the oxidative cyclization of an imine and an alkyne on nickel (0) proceeded quantitatively to give a five-membered aza-nickelacycle, nickelapyrroline, and the insertion of the second alkyne to give a seven-membered aza-nickelacycle, nickeladihydroazepine, for the first time. We also reported that the reductive elimination from the nickeladihydroazepine led to the formation of 1,2-dihydropyridine. Moreover, this sequential reaction process was expanded to a nickel-catalyzed [2+2+2] cycloaddition of two alkynes and an imine to synthesize a 1,2-dihydropyridine. This reaction is the first example of the selective formation of 1,2-dihydropyridine by a transition metal-catalyzed reaction.
The formation of a five-membered oxa-nickelacycle, nickeladihydrofuran, by oxidative cyclization of an alkyne and an aldehyde with nickel (0) was demonstrated for the first time. Moreover, we also demonstrated the transformation of the nickeladihydrofuran into an enone by decomposition, a lactone by carbonylation and an allylic alcohol by treatment with ZnMe_2, which suggests that nickeladihydrofuran is an important intermediate in a variety of catalytic reactions. As an example of oxidative cyclization of a carbonyl group and an alkyne with nickel (0), the reaction of carbon dioxiside and an alkyne with nickel (0) to give a nickelalactone had been reported. Although it is very important work in this field, the nickelalactone can not act as a key inetermediate in mutlicomponent coupling reactions as well as hydroacylation reactions.
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