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Electrophotochemical Ce-Catalyzed Ring-Opening Functionalization of Cycloalkanols under Redox-Neutral Conditions: Scope and Mechanism
时间:2022-08-31 15:29:15点击量:

        Zhaoliang Yang,Dali Yang,Jianye Zhang,Chenyu Tan,Jiajun Li,Shengchun Wang,Heng Zhang,Zhiliang Huang*, and Aiwen Lei*. J. Am. Chem. Soc.(雷爱文,黄志良)

        Abstract:

        Selective cleavage and functionalization of C–C bonds in alcohols is gaining increasing interest in organic synthesis and biomass conversion. In particular, the development of redox-neutral catalytic methods with cheap catalysts and clean energy is of utmost interest. In this work, we report a versatile redox-neutral method for the ring-opening functionalization of cycloalkanols by electrophotochemical (EPC) cerium (Ce) catalysis. The EPC-Ce-enabled catalysis allows for cycloalkanols with different ring sizes to be cleaved while tolerating a broad range of functional groups. Notably, in the presence of chloride as a counteranion and electrolyte, this protocol selectively leads to the formation of C–CN, C–C, C–S, or C–oxime bonds instead of a C–halide bond after β-scission. A preliminary mechanistic investigation indicates that the redox-active Ce catalyst can be tuned by electro-oxidation and photo-reduction, thus avoiding the use of an external oxidant. Spectroscopic characterizations (cyclic voltammetry, UV–vis, electron paramagnetic resonance, and X-ray absorption fine structure) suggest a Ce(III)/Ce(IV) catalytic pathway for this transformation, in which a Ce(IV)-alkoxide is involved.

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        https://pubs.acs.org/doi/abs/10.1021/jacs.2c05520