铜催化下的自由基反应在有机合成中的应用
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摘要
金属试剂或催化剂的发现和发展对有机化学的发展和革新起到决定性作用。众所周知,钯催化体系的发展直接带动了交叉偶联反应乃至整个金属有机导向的有机合成化学的繁荣;近年来,金和银催化多样性化学在有机合成中的兴起和强盛进一步阐释了金属在有机合成转化中所扮演的关键性角色。而且这些例子无不展示了这样的一个规律:基于特定金属的试剂或催化体系大多具有不同于其他金属的独特的反应化学。因此,报告人自独立开展研究工作以来,立足于"开发新型金属有机试剂和催化体系",以实现高效、高选择性且环境友好的有机合成转化为目标。目前我们利用廉价、易得的金属铜盐做催化剂,通过诱导产生氧自由基、磷中心自由基、含氟自由基等,成功实现了若干自由基参与的C-C键活化及切断反应及C-H键的官能团化反应,以及不饱和C-C键的双官能团化反应。
The discovery and development of transition-metal reagents and catalysts played an important and decisive role in the development and revolution of organic chemistry.As we all know,the cross coupling reactions were boomed due to the rapid development of Pd catalysis,which even provided the prosperity of the whole metal-oriented organic synthesis.In recent times,the booming and diversity of Au and Ag catalysis in synthetic organic chemistry further imply their vital roles in transition-metal catalyzed organic transformations.All above examples demonstrate one RULE:special or certain transition metal catalysis possesses unique reactivities.Since I started my independent work in 2013,our research goal has been aimed to develop new synthetic methods with high efficiency,high selectivity(including regio-,chemo-and stereo-selectivity) and good sustainability by the discovery and development of novel organic reagents or transition metal catalysis.So far with inexpensive and readily accessible Cu salts as catalysts,oxygen radicals plus P-centered radicals as well as fluoro-contained radicals have been triggered and difunctionalizations of C-C double bonds and C-C triple bonds as well as activation and cleavage of C-C bonds and C-H bonds have been disclosed.
引文
[1]Qiuling Song*,Qiang Feng and Mingxin Zhou,Org.Lett.2013,15,5990–5993
    [2]Qiuling Song*,Qiang Feng and Kai Yang,Org.Lett.2014,16,624–627
    [3]Xuezhao Xu,Wen Ding,Yuanguang Lin and Qiuling Song*,Org.Lett.2015,17,516–519
    [4]Mingxin Zhou,Ming Chen,Yao Zhou,Kai Yang,Jihu Su,Jiangfeng Du and Qiuling Song*,Org.Lett.2015,17,1786–1789
    [5]Mingxin Zhou,Yao Zhou and Qiuling Song*,Chem.?Eur.J.2015,21,10654–0659
    [6]Yao Zhou,Changqing Rao,Shaoyu Mai and Qiuling Song*,J.Org.Chem.2016,81,2027–2034