Visible-Light-Controlled Ruthenium-Catalyzed Olefin Metathesis.
Visible-Light-Controlled Ruthenium-Catalyzed Olefin Metathesis.
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DOI：
10.1021/jacs.8b13663
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发表时间：
2019-04
影响因子：
15
通讯作者：
Cédric Theunissen;M. A. Ashley;T. Rovis
中科院分区：
文献类型：
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作者：
Cédric Theunissen;M. A. Ashley;T. Rovis
烯烃化合反应现在是建立新的碳-碳键的最有效的方法之一。虽然大多数努力都集中在开发更高效的催化剂上，但最近特别关注开发潜在的化合催化剂，这是一种需要外部刺激才能变得活跃的非活性物种。这增加了对反应的控制，这对材料科学的应用是至关重要的。在这里，我们报告了我们的工作，开发了一种新的体系，通过将烯烃复分解和光氧化还原催化相结合来实现可见光控制的复分解反应。含有两个N-杂环卡宾的Ru歧化催化剂与氧化性的吡咯光催化剂相结合，在仅用可见光作为刺激的情况下提供了良好的时间和空间分辨率。描述了该体系在合成、聚合物图案化和空间分辨开环歧化聚合光刻中的应用。
Olefin metathesis is now one of the most efficient ways to create new carbon-carbon bonds. While most efforts focused on the development of ever-more efficient catalysts, a particular attention has recently been devoted to developing latent metathesis catalysts, inactive species that need an external stimulus to become active. This furnishes an increased control over the reaction which is crucial for applications in materials science. Here, we report our work on the development of a new system to achieve visible-light-controlled metathesis by merging olefin metathesis and photoredox catalysis. The combination of a ruthenium metathesis catalyst bearing two N-heterocyclic carbenes with an oxidizing pyrylium photocatalyst affords excellent temporal and spatial resolution using only visible light as stimulus. Applications of this system in synthesis, as well as in polymer patterning and photolithography with spatially resolved ring-opening metathesis polymerization, are described.