Zhao, Xiaorui; Zhu, Xiaojuan; Wang, Kang; Lv, Junqian; Chen, Shangjun; Yao, Guohua; Lang, Junyu; Lv, Fei; Pu, Yinghui; Yang, Ruoou; Zhang, Bingsen; Jiang, Zheng; Wan, Ying

NATURE COMMUNICATIONS

2022, 13,

Zhao, Xiaorui; Zhu, Xiaojuan; Wang, Kang; Lv, Junqian; Chen, Shangjun; Yao, Guohua; Lang, Junyu; Lv, Fei; Pu, Yinghui; Yang, Ruoou; Zhang, Bingsen; Jiang, Zheng; Wan, Ying

Traditional approaches for transition-metal catalyzed oxidative cross-coupling reactions rely on sp(2)-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(sp(3))-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. Traditional approaches for transition-metal catalyzed oxidative cross-coupling reactions rely on sp(2)-hybridized starting materials. Here the authors report a heterogeneous Pd-catalyzed radical relay method for the conversion of a heteroarene C(sp(3))-H bond into ethers.