-Alkenoxypyridinium salts were found to be highly active electrophilic reagents that could be used to activate the C-N bond of amides. Both aromatic amides and aliphatic amides could be transformed into the corresponding β-oxo esters with good yields via the combined use of -alkenoxypyridinium salts and water. The methodology proceeds under mild reaction conditions and is tolerant of various functional groups in both reaction partners.
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http://dx.doi.org/10.1021/acs.orglett.0c02457 | DOI Listing |
J Org Chem
December 2023
Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, School of Pharmacy, Xuzhou Medical University, Xuzhou 221004, China.
A general, rapid, and scalable method for the preparation of α-halogenated ketones using N-alkenoxypyridinium salts as substrates and quaternary ammonium salts as halogen sources was developed, featuring mild reaction conditions, excellent functional group tolerance, short reaction times, and a wide substrate scope.
View Article and Find Full Text PDFChem Commun (Camb)
March 2023
Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, School of Pharmacy, Xuzhou Medical University, Xuzhou 221004, Jiangsu, China.
An efficient method for the synthesis of 1,4-ketoaldehydes the cross-coupling of -alkenoxyheteroarenium salts and primary aldehydes is developed. This method provides a broad substrate scope and excellent functional group compatibility. The utility of this method is demonstrated the diverse transformations of heterocyclic compounds and cycloheptanone, as well as the late-stage functionalization of biorelevant molecules.
View Article and Find Full Text PDFOrg Lett
September 2020
Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, School of Pharmacy, Xuzhou Medical University, Tongshan Road 209, Xuzhou 221004, China.
-Alkenoxypyridinium salts were found to be highly active electrophilic reagents that could be used to activate the C-N bond of amides. Both aromatic amides and aliphatic amides could be transformed into the corresponding β-oxo esters with good yields via the combined use of -alkenoxypyridinium salts and water. The methodology proceeds under mild reaction conditions and is tolerant of various functional groups in both reaction partners.
View Article and Find Full Text PDFOrg Lett
September 2020
School of Chemical Sciences, University of the Chinese Academy of Sciences, Beijing 100049, China.
N-heterocyclic carbenes (NHCs) are well-known as ligands and organocatalysts, but there is no recognition for their catalytic role as a stabilizer through electrostatic interaction rather than electron donation. By utilizing the electrostatic interaction, we herein describe the success of a visible-light-triggered radical-radical cross-coupling of N-alkenoxypyridinium salts and NaI, giving a variety of α-iodo ketones. Computational studies characterize the stabilization role of NHCs.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2020
Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon, 34141, Republic of Korea.
N-Alkenoxypyridinium salts have been used as synthons for the umpolung reaction of enolates for the preparation of α-functionalized carbonyl compounds. In contrast, we found that the photoreduction of N-alkenoxypyridinium salts generates α-carbonyl radicals after cleavage of the N-O bond, thereby allowing simultaneous incorporation of α-keto and pyridyl groups across unactivated alkenes. In the process, the formed α-carbonyl radicals engage unactivated alkenes to afford alkyl radical intermediates poised for subsequent addition to pyridinium salts, which ultimately affords a variety of γ-pyridyl ketones under mild reaction conditions.
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