Investigation of Reactivities of Electron Deficient Olefins and its Application to Organic Synthesis

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1. Titanium Trichloride Mediated Reduction of Nitro-, and Dicyanoolefins:Aqueous titanium trichloride was found to reduce nitorolefins to pyrroles and/or divinyl amines in moderate yields. Dicyanoolefins were also reduced to give five menbered cyclic eneaminonitriles.2. Electroreduction of Nitroolefins in the Presence of Titanium Tetrachloride:Electroreduction of nitroolefins was achieved in the presence of titanium tetrachloride in DMF to yield corresponding nitriles in high yields. Nitroolefins can be easily prepared by means of condensation of aldehydes with nitromethan, and hence the present reduction offers a new synthetic method of one carbon elongated nitriles from easily available aldehydes.3. High Pressure cycloaddition of FuranThe Diels-Alder reaction of furan with dialkyl acetxymethylenemalonate did not proceed at conventional conditions. However, the reaction took place under high pressure of 1 GPa to give an adduct. 7-oxabicyclo[2.2.1]heptene derivative, from which a precursor of C-ribonucleoside was synthesized stereospecifically in a high yield.