Spin-Selective Generation of Triplet Nitrenes: Olefin Aziridination through Visible-Light Photosensitization of Azidoformates.
Spin-Selective Generation of Triplet Nitrenes: Olefin Aziridination through Visible-Light Photosensitization of Azidoformates.
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DOI：
10.1002/anie.201510868
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发表时间：
2016-02-05
期刊：
影响因子：
--
通讯作者：
Yoon TP
中科院分区：
文献类型：
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作者：
Scholz SO;Farney EP;Kim S;Bates DM;Yoon TP
叠氮甲酸酯是一种很有潜力的氮化物前体，但它们的直接光化学活化可以导致氮杂环化和烯丙基胺化产物的竞争生成。在这里，我们展示了可见光激活的过渡金属络合物可以是三重态增敏剂，通过叠氮甲酸酯的自旋选择光生成三重态硝烯来选择性地生成氮杂环丙烷。该方法可以实现多种烯烃的氮杂环化反应和烯醇醚的羟胺化反应(以烯烃为限制试剂)。制备规模的氮杂环己烷很容易在流动中实现。杂环上的新旋律。合成有用的光化学氮化反应可以通过使用可见光激活的过渡金属光敏剂来产生具有化学选择性的三重态的硝烯来实现。广泛的脂肪族和芳香族烯烃可以很容易地氮化，而不需要竞争性的烯丙基插入反应。
Azidoformates are interesting potential nitrene precursors, but their direct photochemical activation can result in competitive formation of aziridination and allylic amination products. Here, we show that visible light activated transition metal complexes can be triplet sensitizers that selectively produce aziridines via the spin-selective photogeneration of triplet nitrenes from azidoformates. This approach enables the aziridination of a wide range of alkenes and the formal oxyamination of enol ethers using the alkene as the limiting reagent. Preparative scale aziridinations can be easily achieved in flow. A fresh spin on heterocycles. Synthetically useful photochemical aziridinations can be achieved by using a visible light activated transition metal photosensitizer to produce nitrenes exclusively in their chemoselective triplet spin state. A wide range of aliphatic and aromatic alkenes can be readily aziridinated without competitive allylic insertion reactions.