Palladium-Catalyzed Asymmetric Acetoxylative Cyclization/Acyl Transfer Cascade of Alkyne-Tethered Malononitriles with Carboxylic Acids
Palladium-catalyzed asymmetric intermolecular <i>trans</i>-acetoxypalladation/desymmetric cyclization/acyl transfer cascades of alkyne-tethered malononitriles with carboxylic acids have been demonstrated. Such a sequence enables the formation of multifunctionalized nitriles bearing α-all-carbon quaternary stereocenters with a high degree of enantiocontrol with a broad substrate scope. Moreover, synthetic elaborations present these multifunctionalized molecules as promising chiral building blocks. Mechanistic studies illustrate that the cascade process proceeds via a key imine intermediate, and the desymmetric cyclization is the enantio-determining step.
Authors
- Shan-Shan Xun
- Yong‐Gui Zhou (ORCID: https://orcid.org/0000-0002-3321-5521)
- Tong Niu (ORCID: https://orcid.org/0000-0001-5813-4608)
- Bo Wu (ORCID: https://orcid.org/0009-0007-0217-2331)
- Yuqing Bai (ORCID: https://orcid.org/0009-0004-1428-3459)
Institutions
- Dalian Institute of Chemical Physics (CN)
- Chinese Academy of Sciences (CN)
- Institute of Catalysis and Petrochemistry (RU)
- Shanghai Institute of Organic Chemistry (CN)
- University of Chinese Academy of Sciences (CN)
- State Key Laboratory of Organometallic Chemistry
- State Key Laboratory of Catalysis
Publication Details
- Journal
- Organic Letters
- Published
- 2025-02-03
- DOI
- https://doi.org/10.1021/acs.orglett.4c04865
- Citations
- 3
- Primary Topic
- Catalytic C–H Functionalization Methods
- Type
- article
- Field-Weighted Citation Impact
- 2.81
Funders
- National Natural Science Foundation of China
- Natural Science Foundation of Liaoning Province
- Dalian Institute of Chemical Physics
- National Key Research and Development Program of China