Isolation of bis(copper) key intermediates in Cu-catalyzed azide-alkyne "click reaction".
Isolation of bis(copper) key intermediates in Cu-catalyzed azide-alkyne "click reaction".
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DOI：
10.1126/sciadv.1500304
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发表时间：
2015-06
期刊：
影响因子：
13.6
通讯作者：
Bertrand G
中科院分区：
文献类型：
--
作者：
Jin L;Tolentino DR;Melaimi M;Bertrand G
在最流行的“点击化学”反应中，分离出比单核反应更活跃的铜（铜）配合物。叠氮化物与末端炔（CuAAC）的1,3偶极环加成是铜催化的最流行的化学转化之一，其应用范围从材料到生命科学。然而，尽管有许多机理研究，对催化循环关键组分的直接观察仍然缺失。最初，单核物质被认为是活跃的催化剂，但后来，双核复合物出现了。我们报道了先前假设的π，σ-双（铜）乙酰醚和迄今未提及的双（金属）三唑配合物的分离。我们还证明，虽然单铜和双铜配合物促进了CuAAC反应，但双核物质参与了动力学上有利的途径。
Isolation of bis(copper) complexes that are kinetically more active than their mononuclear counterparts in the most popular “click chemistry” reaction. The copper-catalyzed 1,3-dipolar cycloaddition of an azide to a terminal alkyne (CuAAC) is one of the most popular chemical transformations, with applications ranging from material to life sciences. However, despite many mechanistic studies, direct observation of key components of the catalytic cycle is still missing. Initially, mononuclear species were thought to be the active catalysts, but later on, dinuclear complexes came to the front. We report the isolation of both a previously postulated π,σ-bis(copper) acetylide and a hitherto never-mentioned bis(metallated) triazole complex. We also demonstrate that although mono- and bis-copper complexes promote the CuAAC reaction, the dinuclear species are involved in the kinetically favored pathway.