Kim Doyoung, Ju Hyewon, Lee Wooseok, Hong Sungwoo
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Korea
Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS) Daejeon 34141 Korea.
Chem Sci. 2024 Nov 13;15(48):20433-20439. doi: 10.1039/d4sc06723a. eCollection 2024 Dec 11.
Cyclopropanes, valuable C3 building blocks in organic synthesis, possess high strain energy and inherent stability. We present an efficient, environmentally benign 1,3-oxyheteroarylation of aryl cyclopropanes using azine -oxides as bifunctional reagents under visible light irradiation. This metal-free method yields β-pyridyl ketones under mild conditions. Mechanistic studies reveal a photo-induced radical pathway involving single-electron oxidation of both aryl cyclopropanes and azine -oxides, followed by stepwise ring opening. The dual oxidation mechanism accommodates diverse cyclopropane and azine -oxide combinations based on their oxidation potentials. This green chemistry method enhances the synthetic utility of aryl cyclopropanes while introducing an efficient strategy for their difunctionalization. The methodology aligns with sustainable organic synthesis principles, offering an environmentally conscious route to valuable synthetic intermediates.
环丙烷是有机合成中有价值的C3结构单元，具有高张力能和固有稳定性。我们展示了一种高效、环境友好的方法，即在可见光照射下，使用氧化偶氮化合物作为双功能试剂，对芳基环丙烷进行1,3-氧杂芳基化反应。这种无金属方法在温和条件下生成β-吡啶基酮。机理研究揭示了一条光诱导自由基途径，涉及芳基环丙烷和氧化偶氮化合物的单电子氧化，随后是逐步开环。基于它们的氧化电位，双氧化机制适用于多种环丙烷和氧化偶氮化合物的组合。这种绿色化学方法提高了芳基环丙烷的合成效用，同时引入了一种有效的双官能化策略。该方法符合可持续有机合成原则，为有价值的合成中间体提供了一条环境友好的路线。
