Dramatic Mechanistic Change in Acid‐Catalyzed Arylation of Azafulleroids Depending on their Ambident N/C Basicity: Formation of Cyclopentene Centered Pentakisadduct |
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| Authors: | Dr Naohiko Ikuma Yuta Doi Koichi Fujioka Tsubasa Mikie Dr Ken Kokubo Prof Dr Takumi Oshima |
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| Institution: | Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2‐1 Yamadaoka, Suita, Osaka 565‐0871 (Japan), Fax: (+81)?6‐6879‐4593 |
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| Abstract: | Azafulleroid, amino‐bridged 5,6]‐open fullerene, has the ambident N/C basicity of the incorporated enamine moiety. Acid‐catalyzed arylation of N‐substituted azafulleroids proceeded via two types of initial N/C protonation to perform monoarylation or 1,4‐bisarylation for the N‐alkyl substituents and shuttlecock‐type pentakisarylation for the N‐phenyl substituent. The dramatic product change was explained by considering the possible mechanism as well as the DFT computational results. |
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| Keywords: | arylation homogeneous catalysis fullerenes nucleophilic substitution protonation |
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