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Unveiling the Hidden Reactivity in the N‑Heterocyclic Carbene-Catalyzed Aerobic Oxidation of Aldehydes: Unlocking Its Powerful Catalytic Performance

An innovative solution that overcomes the long-standing inherently low efficiency in N-heterocyclic carbene-catalyzed aerobic oxidation of aldehydes is reported. This solution included the design and synthesis of a novel polymerized catalyst and the utilization of a flow reactor. The unprecedentedly...

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Bibliographic Details
Published in:Journal of organic chemistry 2024-12, Vol.89 (24), p.18344-18352
Main Authors: Fan, Chenrui, Zhao, Xu, Gopireddy, Reveendra, Guo, Yueyin, Wang, Junya, Yuan, Jie, Luo, Mei, Shi, Tiejun, Yang, Lixu, He, Jianbo, Luo, Yunfei
Format: Article
Language:English
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Summary:An innovative solution that overcomes the long-standing inherently low efficiency in N-heterocyclic carbene-catalyzed aerobic oxidation of aldehydes is reported. This solution included the design and synthesis of a novel polymerized catalyst and the utilization of a flow reactor. The unprecedentedly high efficiency achieved via this protocol makes it synthetically applicable. A total turnover number (TON) of 26,300 was achieved based on recycling experiments (runs). The highest TON in a single run could be up to 2475 with a turnover frequency (TOF) of 208 h–1, far superior to its traditional counterpart, in which a typical TON ranges from 20 to 100 with a TOF of less than 10 h–1. The catalyst has been recycled over 50 times and is still fully active. The success was attributed to the discovery of hidden reactivity, which was observed for the first time as an autoacceleration in the reaction rate during kinetic investigations. The research also provided concrete evidence supporting the conclusion that radical intermediates played crucial roles in the catalytic cycle by having a determinative impact on the overall reaction rate.
ISSN:0022-3263
1520-6904
1520-6904
DOI:10.1021/acs.joc.4c02199