Copper(I)-catalyzed synthesis of azoles. DFT study predicts unprecedented reactivity and intermediates
Copper(I)-catalyzed synthesis of azoles. DFT study predicts unprecedented reactivity and intermediates
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DOI：
10.1021/ja0471525
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发表时间：
2005-01-12
影响因子：
15
通讯作者：
Fokin, VV
中科院分区：
文献类型：
--
作者：
Himo, F;Lovell, T;Fokin, VV
Huisgen的1,3-偶极环加成物在铜(1)乙酰醚与叠氮化物和腈氧化物反应时变得不协调，分别提供了1,4-二取代1,2,3-三唑和3,4-二取代异恶唑的便捷通道。该过程是高度可靠的，并且在两个组件方面都表现出异常广泛的范围。计算研究揭示了一个涉及前所未有的金属循环中间体的逐步机制，这似乎是各种偶极子的共同之处。
Huisgen's 1,3-dipolar cycloadditions become nonconcerted when copper(l) acetylides react with azides and nitrile oxides, providing ready access to 1,4-disubstituted 1,2,3-triazoles and 3,4-disubstituted isoxazoles, respectively. The process is highly reliable and exhibits an unusually wide scope with respect to both components. Computational studies revealed a stepwise mechanism involving unprecedented metallacycle intermediates, which appear to be common for a variety of dipoles.