Ring-expanding metathesis oligomerization of cyclic nitrones
Ring-expanding metathesis oligomerization of cyclic nitrones
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环硝酮的扩环复分解低聚
DOI：
10.1002/ejoc.201402859
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发表时间：
2014
影响因子：
2.8
通讯作者：
and Takeshi Naota
中科院分区：
文献类型：
--
作者：
Yasushi Imada;Chiaki Okita;Hiroki Maeda;Masayuki Kishimoto;Yoshinori Sugano;Hiroyuki Kaneshiro;Yuri Nishida;Soichiro Kawamorita;Naruyoshi Komiya;and Takeshi Naota
虽然五元和六元环状硝酮的化学研究取得了显著进展，但中型和大型环状硝酮尽管具有作为功能材料的潜力，但仍然未受到影响。在此，我们报告了中等大小的环状硝酮在有机或无机酸的存在下发生扩环二聚/低聚反应，并且我们已经成功表征了一系列高达50元环大小的新型大环聚硝酮。在该反应中观察到了前所未有的环尺寸依赖性特异性，其中具有奇数元环的环状硝酮以高选择性转化为二聚体，而偶数元环经历连续的扩环反应以提供大环聚硝酮。
Although there has been marked progress in the chemistry of five‐ and six‐membered cyclic nitrones, medium‐ and large‐sized cyclic nitrones have remained untouched despite their potential as functional materials. Herein, we report that medium‐sized cyclic nitrones undergo ring‐expanding dimerization/oligomerization in the presence of organic or inorganic acids, and we have successfully characterized a series of novel macrocyclic polynitrones up to a 50‐membered ring size. An unprecedented ring‐size‐dependent specificity was observed for this reaction, in which cyclic nitrones with odd‐number‐membered rings are converted into dimers with high selectivity, whereas even‐number‐membered rings undergo consecutive ring‐expansion reactions to afford macrocyclic polynitrones.