Three‐Dimensional Radical Covalent Organic Frameworks as Highly Efficient and Stable Catalysts for Selective Oxidation of Alcohols

Fengqian Chen , Xinyu Guan , Hui Li , Jiehua Ding , Liangkui S Zhu , Bin Tang , Valentin Valtchev (1) , Yushan Yan , Shilun Qiu , Qianrong Fang

1 LCS - Laboratoire catalyse et spectrochimie

With excellent designability, large accessible inner surface, and high chemical stability, covalent organic frameworks (COFs) are promising candidates as metal-free heterogeneous catalysts. In this work, we, for the first time, report two three-dimensional (3D) radicalbased COFs, termed JUC-565 and JUC-566, in which radical moieties (2,2,6,6-tetramethylpiperidine-1-oxy, TEMPO) are uniformly decorated on the channel walls via a bottom-up approach. Based on grafted functional groups and suitable regular channels, these materials open up the application of COFs as highly efficient and selective metal-free redox catalysts in aerobic oxidation of alcohols to relevant aldehydes or ketones with outstanding turn over frequency (TOF) up to 132 h-1 , which has exceeded other TEMPO-modified catalytic materials tested under similar conditions. Meanwhile, these stable COF-based catalysts could be easily recovered and reused for multiple runs. This study thus promotes 3D functional COFs anchored with stable radicals for potential applications in organic synthesis and material science.

Mots clés: covalent organic frameworks; radical; functionalization; selective; oxidation of alcohol

Domaines: Chimie

Fengqian Chen, Xinyu Guan, Hui Li, Jiehua Ding, Liangkui S Zhu, et al.. Three‐Dimensional Radical Covalent Organic Frameworks as Highly Efficient and Stable Catalysts for Selective Oxidation of Alcohols. Angewandte Chemie, 2021, 133 (41), pp.22404-22409. ⟨10.1002/ange.202108357⟩. ⟨hal-03424272⟩