催化作用
钯
激进的
化学
微型多孔材料
芳基
光化学
甲烷氧化偶联
同种类的
组合化学
协同催化
介孔材料
选择性
卤化物
有机化学
物理
热力学
烷基
作者
Xiaorui Zhao,Xiaojuan Zhu,Kang Wang,Junqian Lv,Shangjun Chen,Guidong Yao,Junyu Lang,Fei Lv,Yunjiao Pu,Ruoou Yang,Bingsen Zhang,Zheng Jiang,Ying Wan
标识
DOI:10.1038/s41467-022-31967-0
摘要
Traditional approaches for transition-metal catalyzed oxidative cross-coupling reactions rely on sp2-hybridized starting materials, such as aryl halides, and more specifically, homogeneous catalysts. We report a heterogeneous Pd-catalyzed radical relay method for the conversion of a heteroarene C(sp3)-H bond into ethers. Pd nanoparticles are supported on an ordered mesoporous composite which, when compared with microporous activated carbons, greatly increases the Pd d charge because of their strong interaction with N-doped anatase nanocrystals. Mechanistic studies provide evidence that electron-deficient Pd with Pd-O/N coordinations efficiently catalyzes the radical relay reaction to release diffusible methoxyl radicals, and highlight the difference between this surface reaction and C-H oxidation mediated by homogeneous catalysts that operate with cyclopalladated intermediates. The reactions proceed efficiently with a turn-over frequency of 84 h-1 and high selectivity toward ethers of >99%. Negligible Pd leaching and activity loss are observed after 7 catalytic runs.
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