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Carboxylic acids are bench-stable and readily available chemical feedstocks that function as optimal and fundamental synthetic platforms for the construction of C(sp)-C(sp) bonds through decarboxylation processes. Herein, a visible light-induced and metal-free strategy for the direct decarboxylative allylic alkylation of Morita-Baylis-Hillman acetates with aliphatic acids was developed. The model delivered a series of trisubstituted alkenes in good to excellent yields. This protocol features broad substrate scope, and mild and redox-neutral conditions.
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http://dx.doi.org/10.1039/d4ob02036g | DOI Listing |
Chem Sci
July 2025
Department of Chemistry, University of Wisconsin-Madison 1101 University Avenue Madison WI 53706 USA
A dual photoredox/hydrogen atom transfer (HAT) strategy for the radical alkoxycarbonylation of allenes is described. Alkoxycarbonyl radicals, generated by photoredox-catalyzed decarboxylation of alkyl oxalic acids, add to the proximal carbon of allene precursors with high regioselectivity to furnish α-allyl-γ-lactone products in up to 92% yield. The intermediate vinyl radicals can be trapped by a hydrogen atom or by a heteroatom using selenium and iodine transfer reagents.
View Article and Find Full Text PDFAcc Chem Res
July 2025
College of Pharmaceutical Science & Collaborative Innovation Center of Yangtze River Delta Region Green Pharmaceuticals, Zhejiang University of Technology, 18 Chaowang Road, Hangzhou 310014, P. R. China.
ConspectusCatalysts drive asymmetric transformations by orchestrating a network of covalent and noncovalent interactions that precisely regulate the reactivity and stereoselectivity. Ion pair catalysis, developed based on the inherent strength and long-range nature of ionic interactions, has demonstrated high catalytic efficiency and broad applicability. While chiral cationic catalysts have long been central to this field, the critical roles of their counteranions have historically been overlooked.
View Article and Find Full Text PDFChemistry
June 2025
School of Chemistry and Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, Victoria, 3010, Australia.
Copper(II) aryl species are proposed intermediates in copper catalysed C-X coupling reactions. Here, the formation and reactions of the cationic copper complexes [(phen)Cu(Ar)] (phen = 1,10-phenanthroline; Ar = Ph, p-MeCH, p-MeOCH, p-MeCOCH) are explored in the gas-phase using electrospray ionisation (ESI) multistage mass spectrometry (MS) experiments in a linear ion trap mass spectrometer together with Density Functional Theory (DFT) calculations. A survey of three routes to the preparation of [(phen)Cu(Ph)] showed that transmetalation of [(phen)Cu][BPh] and desulfination of [(phen)Cu(OSPh)] both produced the desired complex [(phen)Cu(Ph)], but decarboxylation of [(phen)Cu(OCPh)] gave a higher yield with fewer competing side reactions, making it the preferred route to the other aryl complexes [(phen)Cu(Ar)].
View Article and Find Full Text PDFJ Am Chem Soc
July 2025
Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, United States.
Here, we report the light-induced decarboxylative ligand-to-metal charge transfer (LMCT) of Cr(III) carboxylate complexes and demonstrate its applicability toward stereoselective Nozaki-Hiyama-Kishi (NHK) allylation reactions. The critical design element of our reaction was identifying a bipyridyl ligand scaffold that enables a single Cr catalyst to facilitate both photolytic dissociation and aldehyde addition. This approach allows for the direct utilization of carboxylic acids and eliminates the need for external redox reagents.
View Article and Find Full Text PDFACS Electrochem
June 2025
School of Chemistry, University College Dublin, Belfield, Dublin D04 N2E5, Ireland.
The validation of the stereochemical purity of synthesized compounds is a requisite for the fine-chemical industry, particularly in the production of enantiopure drug compounds. However, most methodologies employed in the determination of enantiopurity require carefully chosen chiral GC or HPLC columns, increasing associated cost, analysis time, and complexity. Herein, we present a nanopore-based technology for the determination of enantiopurity, exploiting changes in ion-current rectification of quartz nanopipettes containing an aprotic organic electrolyte.
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