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[摘要]:The one-step reaction of 2,6-dihydroxyphenyl Me ketone and sarcosine with [60]fullerene in refluxing chlorobenzene affords, in a totally regioselective process, the cis-1 bicyclic-fused organofullerene through a new intramol. nucleophilic addn. of one hydroxy group to the fullerene double bond. Exptl. findings reveal the presence of a Me group on C-2 of the pyrrolidine ring as an essential requirement for the cyclization process, whereas the existence of a H-bond between a second hydroxylic group and the nitrogen atom of the pyrrolidine ring seems to favor the approaching geometry without detg. the reaction outcome. Theor. calcns. using the two-layered ONIOM approach and d. functional theory support the exptl. findings, predicting the strong impact that the presence of the Me substituent on the C-2 of the pyrrolidine ring has on the mol. geometry and, hence, on the intramol. cyclization process. |
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