AgN3-Catalyzed Hydroazidation of Terminal Alkynes and Mechanistic Studies,Journal of the American Chemical Society

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AgN3-Catalyzed Hydroazidation of Terminal Alkynes and Mechanistic Studies
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-03-26 , DOI: 10.1021/jacs.0c00836
Shanshan Cao ₁ , Qinghe Ji ₁ , Huaizhi Li ₁ , Maolin Pang ₂ , Haiyan Yuan ₁ , Jingping Zhang ₁ , Xihe Bi _{1,

3}

Affiliation

The hydroazidation of alkynes is the most straightforward way to access vinyl azides - versatile building blocks in organic synthesis. We previously realized such a fundamental reaction of terminal alkynes using Ag2CO3 as a catalyst. However, the high catalyst loading seriously limits its practicality, and moreover the exact reaction mechanism remains unclear. Here, on the basis of X-ray diffraction studies on the conversion of silver salts, we report the identification of AgN3 as the real catalytic species in this reaction, and therefore developed a AgN3-catalyzed hydroazidation of terminal alkynes. AgN3 proved to be a highly robust catalyst, as the loading of AgN3 could be as low as 5 mol%, and such a small proportion of AgN3 is still highly efficient even at a 50 mmol reaction scale. Further, the combination of experimental investigations and theoretical calculations disclosed that the concerted addition mechanism via a six-membered transition state is more favored than the classical silver acetylide mechanism.

中文翻译：

AgN3 催化的末端炔烃的氢叠氮化反应和机理研究

炔烃的加氢叠氮化是获得乙烯基叠氮化物的最直接方式——有机合成中的通用构件。我们以前使用 Ag2CO3 作为催化剂实现了末端炔烃的这种基本反应。然而，高催化剂负载严重限制了其实用性，而且确切的反应机理尚不清楚。在这里，基于对银盐转化的 X 射线衍射研究，我们报告了 AgN3 作为该反应中真正的催化物种的鉴定，因此开发了 AgN3 催化的末端炔烃的氢叠氮化反应。AgN3 被证明是一种非常稳定的催化剂，因为 AgN3 的负载量可以低至 5 mol%，即使在 50 mmol 的反应规模下，如此小比例的 AgN3 仍然是高效的。更多，

更新日期：2020-03-26

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