Site-Selective Remote Radical C-H Functionalization of Unactivated C-H Bonds in Amides Using Sulfone Reagents.
Site-Selective Remote Radical C-H Functionalization of Unactivated C-H Bonds in Amides Using Sulfone Reagents.
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DOI：
10.1002/anie.201807455
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发表时间：
2018-08
影响因子：
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通讯作者：
Yong Xia;Lin Wang;A. Studer
中科院分区：
文献类型：
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作者：
Yong Xia;Lin Wang;A. Studer
介绍了一种利用自由基化学对各种酰胺中未活化的脂肪族C-H键进行远距离定点功能化的通用和实用的策略。通过使用容易安装的N-烯丙基磺酰基部分作为N-自由基前体来实现C-H键官能化。原位生成的N-自由基参与分子内1，5-氢原子转移以生成易位的C自由基，其随后被各种砜试剂捕获以提供相应的C-H官能化酰胺。该方法的通用性通过成功的远程C-N3、C-Cl、C-Br、C-SCF 3、C-SPh和C-C键形成来证明。未活化的三级和二级C-H键以及活化的一级C-H键可以通过这种方法容易地官能化。
A general and practical strategy for remote site-selective functionalization of unactivated aliphatic C-H bonds in various amides by radical chemistry is introduced. C-H bond functionalization is achieved by using the readily installed N-allylsulfonyl moiety as an N-radical precursor. The in situ generated N-radical engages in intramolecular 1,5-hydrogen atom transfer to generate a translocated C radical which is subsequently trapped with various sulfone reagents to afford the corresponding C-H functionalized amides. The generality of the approach is documented by the successful remote C-N3 , C-Cl, C-Br, C-SCF3 , C-SPh, and C-C bond formation. Unactivated tertiary and secondary C-H bonds, as well as activated primary C-H bonds, can be readily functionalized by this method.