過渡金屬催化含氮化合物與碳六十的反應探討:合成創新的碳六十衍生物

Abstract

Developments of three new methods for fullerene functionalization through transition metal catalysis are presented. Palladium-catalyzed heteroannulation of [60]fullerene with N-substituted benzamides, which proceeds through direct sp2 C–H bond activation to form 7-membered ring pallada-intermediate with C60, led to formation of [60]fulleroisoquinolinones in moderate to good yields 8–64% based on recovered C60. C–H bond activation is highly regioselective in this reaction. An efficient palladium-catalyzed chelating-group-assisted C−H activation of N-sulfonyl-2-aminobiaryls and their annulations with [60]fullerene via sequential C–C and C–N bond formation at room temperature to afford [60]fulleroazepines is demonstrated for the first time. The formation [60]fulleroazepines is highly regioselective and tolerance to both electron-withdrawing and electron-donating groups on the aryl moiety with good monofuctionalized fullerene reaction yield (up to 51% isolated yield and 85% based on recovered C60). A system with ingredients of late transition-metal halides, phosphines, water and reducing agent in 1,2-dichlorobenzene can efficiently catalyze the intermolecular reductive coupling of [60]fullerene with N-sulfonylaldimines to afford novel 1,2-hydrobenzylated [60]fullerene derivatives. A control experiment in the absence of aldimines produced C60H2, which proved that the reaction could proceed via a [60]fullerene metal complex, M(η2-C60)(ligand). An isotope labeling experiment with D2O as deuterio source resulted in deuteriobenzylation with deterium bonded to the sp3-carbon of C60, providing evidence of a five-membered azametallacycle intermediate. Evaluation of the scope of reductive coupling reaction with versatile aldimines gave access to the novel hydrobenzylated products. All the reductive coupling products were completely characterized by infrared and NMR spectroscopy and ESI-mass spectrometry. Based on these results, a possible reaction mechanism is proposed. Synthesized series of open-cage fullerene derivatives possessing with N-alkylmaleimide moiety as n-type materials for organic solar cells.

Developments of three new methods for fullerene functionalization through transition metal catalysis are presented. Palladium-catalyzed heteroannulation of [60]fullerene with N-substituted benzamides, which proceeds through direct sp2 C–H bond activation to form 7-membered ring pallada-intermediate with C60, led to formation of [60]fulleroisoquinolinones in moderate to good yields 8–64% based on recovered C60. C–H bond activation is highly regioselective in this reaction. An efficient palladium-catalyzed chelating-group-assisted C−H activation of N-sulfonyl-2-aminobiaryls and their annulations with [60]fullerene via sequential C–C and C–N bond formation at room temperature to afford [60]fulleroazepines is demonstrated for the first time. The formation [60]fulleroazepines is highly regioselective and tolerance to both electron-withdrawing and electron-donating groups on the aryl moiety with good monofuctionalized fullerene reaction yield (up to 51% isolated yield and 85% based on recovered C60). A system with ingredients of late transition-metal halides, phosphines, water and reducing agent in 1,2-dichlorobenzene can efficiently catalyze the intermolecular reductive coupling of [60]fullerene with N-sulfonylaldimines to afford novel 1,2-hydrobenzylated [60]fullerene derivatives. A control experiment in the absence of aldimines produced C60H2, which proved that the reaction could proceed via a [60]fullerene metal complex, M(η2-C60)(ligand). An isotope labeling experiment with D2O as deuterio source resulted in deuteriobenzylation with deterium bonded to the sp3-carbon of C60, providing evidence of a five-membered azametallacycle intermediate. Evaluation of the scope of reductive coupling reaction with versatile aldimines gave access to the novel hydrobenzylated products. All the reductive coupling products were completely characterized by infrared and NMR spectroscopy and ESI-mass spectrometry. Based on these results, a possible reaction mechanism is proposed. Synthesized series of open-cage fullerene derivatives possessing with N-alkylmaleimide moiety as n-type materials for organic solar cells.