Regioselective synthesis of 1,4-di(organo)[60]fullerenes through DMF-assisted monoaddition of silylmethyl Grignard reagents and subsequent alkylation reaction.
Regioselective synthesis of 1,4-di(organo)[60]fullerenes through DMF-assisted monoaddition of silylmethyl Grignard reagents and subsequent alkylation reaction.
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DOI：
10.1021/ja8041299
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发表时间：
2008-10
影响因子：
15
通讯作者：
Y. Matsuo;A. Iwashita;Yoko Abe;Chang-Zhi Li;K. Matsuo;M. Hashiguchi;E. Nakamura
中科院分区：
文献类型：
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作者：
Y. Matsuo;A. Iwashita;Yoko Abe;Chang-Zhi Li;K. Matsuo;M. Hashiguchi;E. Nakamura
格氏试剂，特别是三（有机）硅甲基氯化镁，在二甲基甲酰胺存在下顺利地加成[60]富勒烯，生成（有机）（氢）[60]富勒烯C60R(1)H，收率很高（分离收率高达93%）。然后将氢富勒烯去质子化生成相应的阴离子C60R(-)，然后将阴离子C60R（-）烷基化得到58pi电子二（有机）[60]富勒烯C60R(1)R(2)，收率很高（总收率高达93%）。两步法提供了各种各样的1,4-二（有机）[60]富勒烯，在[60]富勒烯核心上具有相同或不同的有机加成。通过改变加数，可以在分子和体积水平上控制化合物的化学和物理性质。
Monoaddition of Grignard reagents, in particular tri(organo)silylmethylmagnesium chlorides, to [60]fullerene took place smoothly in the presence of dimethylformamide to produce (organo)(hydro)[60]fullerenes, C60R(1)H, in good yield (up to 93% isolated yield). The hydrofullerene was then deprotonated to generate the corresponding anion, C60R(-), which was then alkylated to obtain 58pi-electron di(organo)[60]fullerenes, C60R(1)R(2), in good to high yield (up to 93% overall yield). The two-step methodology provides a wide variety of 1,4-di(organo)[60] fullerenes bearing the same or different organic addends on the [60] fullerene core. By changing the addends, one can control the chemical and physical properties of the compounds at the molecular and bulk levels.