Highly Regioselective Synthesis of Bis-Aziridino[60]fullerene with Sulfilimine
Highly Regioselective Synthesis of Bis-Aziridino[60]fullerene with Sulfilimine
复制标题
硫亚胺高区域选择性合成双氮丙啶基[60]富勒烯
DOI：
10.1002/asia.201000244
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
S.Naga
中科院分区：
文献类型：
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作者：
M.Okada;T.Nakahodo;M.O.Ishitsuka;H.Nikawa;T.Tsuchiya;T.Akasaka;T.Fujie;T.Yoshimura;Z.Slanina;S.Naga
在我们研究富勒烯叠氮化合成方法的发展过程中，我们最近报道了由亚砜胺生成的硝基烯与c60的光化学[2+1]环加成反应。众所周知，在N原子上有一个供电子基团的亚胺会发生迈克尔型反应，随后伴随着硫化物的消除，生成相应的叠氮嘧啶。在这些反应中，亚亚胺对亲电烯烃起亲核试剂的作用。此外，c60还具有低LUMO能级和电子接受特性。因此，它可以是亲电烯烃。在这种情况下，亚砜胺可能与c60反应生成相应的叠氮二烯。我们研究了（S，S） -二苯基亚胺与c60的热反应和区域选择性合成的二和三叠氮化富勒烯。这些结构是通过光谱分析确定的。其中，用单晶X射线分析测定了二叠氮化[60]富勒烯C60(NCH3)2的结构。结果表明，多叠氮化反应只发生在c60的同一六元环上，形成双加合物和三加合物的同分异构体。
In the course of our study of the development of a synthetic methodology for the aziridination of fullerenes, we recently reported the photochemical [2+1] cycloaddition reaction of nitrene onto C60generated from sulfilimine. Sulfilimines with an electron‐donating group on the N atom are well known to undergo Michael‐type reactions, followed by concomitant elimination of sulfide to afford the corresponding aziridines. In these reactions, sulfilimines act as a nucleophile to the electrophilic olefins. Furthermore, C60has characteristic features of a low LUMO level and electron‐accepting properties. Therefore, it can be an electrophilic olefin. In this context, sulfilimines might react with C60to afford the corresponding aziridinofullerenes. We have studied the thermal reaction of (S,S)‐diphenylsulfilimines with C60and regioselectively synthesized bis‐ and tris‐aziridinated fullerenes. These structures were determined through spectroscopic analyses. Among these, the structure of bis‐aziridinated[60]fullerene, C60(NCH3)2, was determined using single‐crystal X‐ray analysis. Results show that the multi‐aziridination occurs exclusively at the same six‐membered ring of C60to afford one isomer of the bis‐adduct and tris‐adduct.