Reductive N-Heterocyclic Carbene Catalysis via Hydride Transfer: Generating Homoenolates from Unsaturated Esters
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.
Authors
- Pengcheng Zheng (ORCID: https://orcid.org/0000-0002-3575-4502)
- Yonggui Robin (ORCID: https://orcid.org/0000-0003-0573-257X)
- Mingyi Pan
- Qingyun Wang (ORCID: https://orcid.org/0009-0007-0402-8587)
Institutions
- Nanyang Technological University (SG)
- Guizhou University (CN)
Publication Details
- Journal
- Organic Letters
- Published
- 2025-05-27
- DOI
- https://doi.org/10.1021/acs.orglett.5c01604
- Primary Topic
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Research Foundation Singapore
- Ministry of Education - Singapore
- Nanyang Technological University
- National Natural Science Foundation of China
- Guizhou University
- National Key Research and Development Program of China
- Project 211