Merging Photochemistry with Electrochemistry: Functional-Group Tolerant Electrochemical Amination of C(sp3 )-H Bonds.
Merging Photochemistry with Electrochemistry: Functional-Group Tolerant Electrochemical Amination of C(sp3 )-H Bonds.
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DOI：
10.1002/anie.201813960
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发表时间：
2019-03
影响因子：
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通讯作者：
Fei Wang;S. Stahl
中科院分区：
文献类型：
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作者：
Fei Wang;S. Stahl
由于氮杂环和胺在药物和天然产物中的普遍存在，C（sp3）-H键的直接胺化在C-H官能化领域引起了广泛的兴趣。本文报道了一种电化学/光化学联用的方法，该方法对sp2和sp3 N-H键都具有良好的反应活性。结果显示了如何使用碘化物作为电化学介体，结合光诱导的中间体N-I键的裂解，使电化学过程在低电极电位下进行。这种方法显著改善了电化学C-H胺化的官能团相容性，例如，容许在高电极电位存在下经历有害副反应的富电子芳族基团。
Direct amination of C(sp3 )-H bonds is of broad interest in the realm of C-H functionalization because of the prevalence of nitrogen heterocycles and amines in pharmaceuticals and natural products. Reported here is a combined electrochemical/photochemical method for dehydrogenative C(sp3 )-H/N-H coupling that exhibits good reactivity with both sp2 and sp3 N-H bonds. The results show how use of iodide as an electrochemical mediator, in combination with light-induced cleavage of intermediate N-I bonds, enables the electrochemical process to proceed at low electrode potentials. This approach significantly improves the functional-group compatibility of electrochemical C-H amination, for example, tolerating electron-rich aromatic groups that undergo deleterious side reactions in the presence of high electrode potentials.