Spatial and temporal control of the alkyne-azide cycloaddition by photoinitiated Cu(II) reduction
Spatial and temporal control of the alkyne-azide cycloaddition by photoinitiated Cu(II) reduction
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DOI：
10.1038/nchem.980
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发表时间：
2011-03-01
期刊：
影响因子：
21.8
通讯作者：
Bowman, Christopher N.
中科院分区：
文献类型：
--
作者：
Adzima, Brian J.;Tao, Youhua;Bowman, Christopher N.
点击反应范式侧重于开发和实施反应，这些反应易于执行，同时具有健壮性，并提供对反应及其产物的精细控制。铜催化的炔叠氮化反应(CuAAC)可以说是这些反应中最多产和最有效的反应，在越来越多的合成方法和应用中普遍存在，包括生物偶联、标记、表面功能化、树枝状大分子合成、聚合物合成和聚合物修饰。遗憾的是，由于铜(I)催化剂通常是通过将铜(II)化学还原为铜(I)而生成的，或者以铜(I)盐的形式添加，因此不容易实现对CuAAC反应的时间和空间控制。在这里，我们展示了CuAAC反应的催化作用，通过铜(II)的光化学还原为铜(I)，提供了使用标准光刻技术对CuAAC反应进行全面的空间和时间控制。结果表明，该技术在小分子合成、图案化材料制备和图案化化学修饰方面具有多种能力。
The click reaction paradigm is focused on the development and implementation of reactions that are simple to perform while being robust and providing exquisite control of the reaction and its products. Arguably the most prolific and powerful of these reactions, the copper-catalysed alkyne-azide reaction (CuAAC) is highly efficient and ubiquitous in an ever increasing number of synthetic methodologies and applications, including bioconjugation, labelling, surface functionalization, dendrimer synthesis, polymer synthesis and polymer modification. Unfortunately, as the Cu(I) catalyst is typically generated by the chemical reduction of Cu(II) to Cu(I), or added as a Cu(I) salt, temporal and spatial control of the CuAAC reaction is not readily achieved. Here, we demonstrate catalysis of the CuAAC reaction via the photochemical reduction of Cu(II) to Cu(I), affording comprehensive spatial and temporal control of the CuAAC reaction using standard photolithographic techniques. Results reveal the diverse capability of this technique in small molecule synthesis, patterned material fabrication and patterned chemical modification.