Electrochemical Diazidation of Alkenes Catalyzed by Manganese Porphyrin Complexes with Second-Sphere Hydrogen-Bond Donors
Electrochemical Diazidation of Alkenes Catalyzed by Manganese Porphyrin Complexes with Second-Sphere Hydrogen-Bond Donors
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DOI：
10.1021/acscatal.2c05186
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发表时间：
2022-11
期刊：
影响因子：
12.9
通讯作者：
Luiz F. T. Novaes;Yi Wang;Jinjian Liu;Xavier Riart-Ferrer;Wan-Chen Cindy Lee;Niankai Fu;J. S. Ho;X. Zhang;Song Lin
中科院分区：
文献类型：
--
作者：
Luiz F. T. Novaes;Yi Wang;Jinjian Liu;Xavier Riart-Ferrer;Wan-Chen Cindy Lee;Niankai Fu;J. S. Ho;X. Zhang;Song Lin
在这项工作中，我们报道了用于叠氮化钠与烯烃的邻位重氮化反应的锰卟啉配合物。与我们以前使用MnBr2催化的工作相比，该协议在以下方面显示出更好的实用性：(1)它需要的催化剂负载量大大减少(低至0.3mol%)，这减少了金属叠氮化合物的形成，并简化了产品纯化；(2)引入中性水缓冲液防止了有毒联苯的产生，有助于更安全的实验过程；(3)催化体系对未活化的末端烯烃表现出更高的反应性。机理研究支持第二球氢键供体在稳定关键反应中间体中的作用。
In this work, we report manganese porphyrin complexes for the electrocatalytic vicinal diazidation of alkenes with sodium azide. This protocol shows improved practicality over our previous work using MnBr2catalysis in the following aspects: (1) it requires substantially lower catalyst loading (as low as 0.3 mol %), which reduces the formation of metal azide complexes and simplifies product purification; (2) the introduction of a neutral aqueous buffer prevents the generation of toxic hydrazoic acid, contributing to a safer experimental procedure; (3) the catalytic system displays improved reactivity toward unactivated terminal alkenes. Mechanistic studies support the roles of second-sphere hydrogen-bond donors in stabilizing key reaction intermediates.