TY - JOUR
T1 - Reductive N-Heterocyclic Carbene Catalysis via Hydride Transfer
T2 - Generating Homoenolates from Unsaturated Esters
AU - Pan, Mingyi
AU - Wang, Qingyun
AU - Zheng, Pengcheng
AU - Chi, Yonggui Robin
N1 - Publisher Copyright:
© 2025 American Chemical Society.
PY - 2025
Y1 - 2025
N2 - In N-heterocyclic carbene (NHC) catalysis, the reduction of NHC-bound acyl azolium species is achieved with progress limited to the generation of ketyl radical intermediates. Here, we report a novel NHC-catalyzed reductive mode for acyl azolium intermediates, which accept a hydride to generate the Breslow intermediate. Then, the reaction of the Breslow intermediate with chalcone results in the formation of cyclopentene, demonstrating a classic umpolung transformation. We expect that this catalytic reductive mode will open new avenues for synthetic transformations.
AB - In N-heterocyclic carbene (NHC) catalysis, the reduction of NHC-bound acyl azolium species is achieved with progress limited to the generation of ketyl radical intermediates. Here, we report a novel NHC-catalyzed reductive mode for acyl azolium intermediates, which accept a hydride to generate the Breslow intermediate. Then, the reaction of the Breslow intermediate with chalcone results in the formation of cyclopentene, demonstrating a classic umpolung transformation. We expect that this catalytic reductive mode will open new avenues for synthetic transformations.
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U2 - 10.1021/acs.orglett.5c01604
DO - 10.1021/acs.orglett.5c01604
M3 - Article
AN - SCOPUS:105006667407
SN - 1523-7060
JO - Organic Letters
JF - Organic Letters
ER -