Catalyst free, visible-light promoted photoaddition reactions between C60 and N-trimethylsilylmethyl-substituted tertiary amines for synthesis of aminomethyl-1,2-dihydrofullerenes
Catalyst free, visible-light promoted photoaddition reactions between C60 and N-trimethylsilylmethyl-substituted tertiary amines for synthesis of aminomethyl-1,2-dihydrofullerenes
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DOI：
10.1016/j.tet.2017.11.064
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发表时间：
2018-01-18
期刊：
影响因子：
2.1
通讯作者：
Mariano, Patrick S.
中科院分区：
文献类型：
--
作者：
Lim, Suk Hyun;Cho, Dae Won;Mariano, Patrick S.
发展了一种高效、温和的氨甲基取代富勒烯的制备方法。该方法，包括无催化剂，可见光照射的10%EtOH-甲苯溶液含有富勒烯C-60和N-三甲基甲硅烷基甲基取代的胺，通过使用20 W的紧凑型荧光灯，导致形成的氨甲基取代的富勒烯加合物在一个非常有效的方式。光加成反应通过由C-60的可见光吸收引发的途径发生，然后从胺到C-60的三重激发态进行SET。乙醇促进的最小自由基的脱甲硅烷基化然后产生相应的α-氨基自由基，其与C-60自由基阴离子偶联以形成富勒烯加合物的阴离子前体。这种利用可见光的新方法在温和的条件下进行，不需要使用光催化剂。因此，在这项努力中开发的方法可以拓宽可以容易地制备的官能化富勒烯衍生物的范围。(C)2017爱思唯尔有限公司版权所有
An efficient and benign method for the preparation of aminomethyl-substituted fullerenes has been developed. The process, involving catalyst free, visible-light irradiation of 10% EtOH-toluene solutions containing fullerene C-60 and N-trimethylsilylmethyl-substituted amines by using a 20 W compact fluorescent lamp, leads to formation of aminomethyl-substituted fullerene adducts in a highly efficient manner. The photoaddition reaction takes place via a pathway initiated by visible light absorption by C-60, followed by SET from the amine to the triplet excited state of C-60. Ethanol-promoted desilylation of the resulting a minimum radical then generates the corresponding alpha-amino radical which couples with the C-60 radical anion to form the anion precursor of the fullerene adducts. The new approach using visible-light takes place under mild conditions and it does not require the use of photocatalysts. Thus, the method developed in this effort could broadens the range of functionalized fullerene derivatives that can be readily prepared. (C) 2017 Elsevier Ltd. All rights reserved.