An efficient copper-catalyzed radical decarboxylative imidation reaction is presented. This strategy is carried out through the copper(i)-catalyzed decarboxylative C(sp(3))-N and C(sp(2))-N coupling of carboxylic acids with N-fluoroarylsulfonimides. The reaction shows good functional group tolerance and it provides a new approach for decarboxylative imidation. Preliminary mechanistic studies of this transformation suggest an involvement of N-centered radical species.
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http://dx.doi.org/10.1039/c6cc03227c | DOI Listing |
J Hazard Mater
December 2024
State Key Laboratory for Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China. Electronic address:
J Org Chem
July 2023
Department of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang 414006, China.
An efficient strategy for visible-light-promoted decarboxylative alkylation of vinylcyclopropanes with alkyl -(acyloxy)phthalimide esters through the dual C-C bond and single N-O bond cleavage, employing triphenylphosphine and lithium iodide as the photoredox system to synthesize 2-alkylated 3,4-dihydronaphthalenes, has been established. This alkylation/cyclization involves a radical process and undergoes a sequence of -(acyloxy)phthalimide ester single-electron reduction, N-O bond cleavage, decarboxylative, alkyl radical addition, C-C bond cleavage, and intramolecular cyclization. Moreover, using the photocatalyst Na-Eosin Y instead of triphenylphosphine and lithium iodide, the vinyl transfer products are acquired when vinylcyclobutanes or vinylcyclopentanes are utilized as alkyl radical receptors.
View Article and Find Full Text PDFJ Am Chem Soc
May 2023
Department of Medicinal Chemistry, College of Pharmacy, University of Michigan, Ann Arbor, Michigan 48109, United States.
Amines and carboxylic acids are abundant synthetic building blocks that are classically united to form an amide bond. To access new pockets of chemical space, we are interested in the development of amine-acid coupling reactions that complement the amide coupling. In particular, the formation of carbon-carbon bonds by formal deamination and decarboxylation would be an impactful addition to the synthesis toolbox.
View Article and Find Full Text PDFMacromol Rapid Commun
May 2022
Institute for Chemical Technology and Polymer Chemistry (ITCP), Karlsruhe Institute of Technology (KIT), Engesserstraße 18, 76131, Karlsruhe, Germany.
Herein the decarboxylation of poly[N-(acryloyloxy)phthalimide] (PAP) for the synthesis of functionalized polymers is reported. PAP homopolymer and block copolymers are used as precursor polymers for the straightforward functionalization via decarboxylation and subsequent Michael-type addition or nitroxide radical coupling (NRC).
View Article and Find Full Text PDFChem Commun (Camb)
September 2021
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China.
-(Acyloxy)phthalimide and oxime derivatives containing N-O bonds are important chemicals and synthetic intermediates, and visible light photoredox reductions of the N-O bonds provide carbon- or nitrogen-centered radicals for -(acyloxy)phthalimide derivatives and iminyl radicals for oxime derivatives. This feature article summarises the recent progress in the visible light photoredox organic reactions, including decarboxylative addition reactions, alkylation, allylation, alkenylation, alkynylation, arylation, heteroarylation and cascade annulation of -(acyloxy)phthalimide derivatives through the formation of carbon-carbon bonds, decarboxylative borylation, amination, oxygenation, sulfuration, selenylation, fluorination and iodination of -(acyloxy)phthalimide derivatives through the formation of carbon-heteroatom bonds, and additions to arenes and alkenes, hydrogen atom transfer and the cleavage of α-carbon-carbon bonds the iminyl radical intermediates for oxime derivatives.
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