Catalytic reductive ring opening of epoxides enabled by zirconocene and photoredox catalysis
Catalytic reductive ring opening of epoxides enabled by zirconocene and photoredox catalysis
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通过二茂锆和光氧化还原催化实现环氧化物的催化还原开环
DOI：
10.1016/j.chempr.2022.04.010
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发表时间：
2022
期刊：
影响因子：
23.5
通讯作者：
Yamaguchi Junichiro
中科院分区：
文献类型：
--
作者：
Aida Kazuhiro;Hirao Marina;Funabashi Aiko;Sugimura Natsuhiko;Ota Eisuke;Yamaguchi Junichiro
环氧化物的还原开环是一种强大的转化，可以将易于获得的环氧化物转化为各种有价值的醇，包括药物、农用化学品和功能聚合物。虽然取得了重大进展，但现有的方法仅限于二茂钛催化反应。在此，我们报道了一种前所未有的由氧化锆催化的环氧化物开环的光氧化还原催化。与传统的开环方法相比，本方案表现出反向区域选择性，通过假定的不稳定自由基提供更多的取代醇。这一反应非常温和，并能顺利地在具有多种官能团的分子中切割C-O键，包括天然产物。我们认为，改变茂金属中心影响开环能量分布的发现是一个重大的进展，并为IV族金属的自由基化学提供了新的视角。
The reductive ring opening of epoxides is a powerful transformation to convert readily accessible epoxides into a diverse array of valuable alcohols, including pharmaceuticals, agrochemicals, and functional polymers. Although significant progress has been made, the established methods were limited to titanocene-catalyzed reactions. Herein, we report an unprecedented zirconocene-catalyzed ring opening of epoxide enabled by photoredox catalysis. Compared with the conventional ring-opening methods, the present protocol exhibited reverse regioselectivity to afford more substituted alcohols via putative less-stable radicals. This reaction is remarkably mild and smoothly cleaves C–O bonds in molecules with a variety of functional groups, including natural products. We believe that the finding that changing the metal center in metallocene influences the energy profile of ring opening is a significant advance and provides a new perspective in radical chemistry with group IV metals.