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通过光氧化还原诱导的 -二氟环丙烷的超共轭环开环反应合成 α-二氟亚甲基醚。

Synthesis of α-Difluoromethylene Ethers via Photoredox-Induced Hyperconjugative Ring Opening of -Difluorocyclopropanes.

机构信息

School of Chemistry, Engineering Research Center of Energy Storage Materials and Devices, Ministry of Education, Xi'an Key Laboratory of Sustainable Energy Material Chemistry, Xi'an Jiaotong University, Xi'an 710049, China.

Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai 200032, China.

出版信息

J Org Chem. 2023 Mar 17;88(6):3787-3793. doi: 10.1021/acs.joc.2c03062. Epub 2023 Feb 24.

Abstract

Fluorinated compounds have found widespread applications in pharmaceuticals, agrochemicals, and materials science. Precise construction of α-difluoromethylene ether (CFO) moiety in organic molecules is of high demand. Herein, a visible light-promoted reaction protocol for the synthesis of α-difluoromethylene ether from -difluorocyclopropane is described. The key ring-opening step is induced by hyperconjugative interaction of cyclopropane with photo-oxidized aromatic rings. This reaction is easy scale-up, and the products bearing a synthetic handle enable their further manipulation.

摘要

氟化合物在制药、农化和材料科学领域有广泛的应用。在有机分子中精确构建α-二氟亚甲基醚(CFO)部分的需求很高。本文描述了一种从 -二氟环丙烷合成α-二氟亚甲基醚的可见光促进反应方案。关键的开环步骤是由环丙烷与光氧化芳环的超共轭相互作用诱导的。该反应易于放大,并且带有合成手柄的产物可以进一步进行操作。

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