Phosphine-catalysis has been developed as the powerful synthetic methodology for carbon-carbon and carbon-hetero bond formation. Carbo- or heterocyclic architectures and asymmetric compounds can be prepared with this approach efficiently. In this context, the catalytic reactions generally proceed through initial phosphine 1,4-addition toward alkenoates, alkynoates or allenoates. Recently, we report a three-component reaction, initiated by nucleophilic attack of phosphines at a(d')-carbon of dialkyl enynoates (1,6-addition), leading to formation ?-lactones. Our continuing interests inspire us to explore another enynoates for realizing addition patterns toward phosphines and prepare useful materials for green-energy applications. Herein, a phosphine-catalyzed [3+2] cycloaddition of (E)-alkyl 5-substituted phenylpent-4-en-2-ynoate with [60]fullerene is revealed. This novel reaction undergoes through initial nucleophilic 1,3-addition of phosphine to a-carbon of enynoates that forms reactive 1,3-dipoles followed by cycloaddition with [60]fullerene. The condition optimization, reaction scope, characterization and mechanism related to the formation of the proposed [60]fullerene products will be presented. The structures of these substrates are characterized spectrometrically and supported by single crystal X-ray diffraction analysis. Further, the isolated fullerene derivatives for application as n-type materials in efficient organic photovoltaics will also be demonstrated.

Phosphine-catalyzed cycloaddition of enynoates with [60]fullerene via initial phosphines 1,3-addition to enynoates

248th National Meeting (2014)

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