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 Zhu; Bin Tang; Valentin Valtchev; Yushan Yan; Shilun Qiu; Qianrong Fang

doi:10.1002/anie.202108357

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

Angew Chem Int Ed Engl. 2021 Oct 4;60(41):22230-22235. doi: 10.1002/anie.202108357. Epub 2021 Sep 1.

Authors

Fengqian Chen¹, Xinyu Guan¹, Hui Li¹, Jiehua Ding¹, Liangkui Zhu¹, Bin Tang², Valentin Valtchev^{3

4}, Yushan Yan⁵, Shilun Qiu¹, Qianrong Fang¹

Affiliations

¹ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, 130012, China.
² Deakin University, Institute for Frontier Materials, Geelong, Victoria, 3216, Australia.
³ Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 189 Song Ling Rd, Qingdao, Shandong, 266101, China.
⁴ Normandie Univ, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, 6 Marechal Juin, 14050, Caen, France.
⁵ Department of Chemical and Biomolecular Engineering, Center for Catalytic Science and Technology, University of Delaware, Newark, DE, 19716, USA.

PMID: 34387410
DOI: 10.1002/anie.202108357

Abstract

With excellent designability, large accessible inner surface, and high chemical stability, covalent organic frameworks (COFs) are promising candidates as metal-free heterogeneous catalysts. Here, we report two 3D radical-based COFs (JUC-565 and JUC-566) in which radical moieties (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. These stable COF-based catalysts could be easily recovered and reused for multiple runs. This study promotes potential applications of 3D functional COFs anchored with stable radicals in organic synthesis and material science.

Keywords: alcohol oxidation; covalent organic frameworks; functionalization; radicals; selectivity.

Abstract

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