Via light irradiation, cross-dehydrogenative coupling of quinolines with alcohols and ethers was achieved under mild conditions. A stoichiometric amount of HCl and room temperature were necessary to promote the reaction. A green Minisci-type cross-dehydrogenative coupling reaction was performed without an oxidant or a transition-metal catalyst.
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http://dx.doi.org/10.1021/acs.joc.4c01620 | DOI Listing |
ACS Omega
December 2024
N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation.
The electrochemically induced reaction between alkenes, bearing an allylic hydrogen atom, and -hydroxyphthalimide was investigated. Cross-dehydrogenative C-O coupling with phthalimide--oxyl radical, derived from -hydroxyphthalimide, occurs instead of oxidation of the allylic site, with the formation of a carbonyl group or functionalization of the double C=C bond. The discovered transformation proceeds in an undivided electrochemical cell equipped with a carbon felt anode and a platinum cathode.
View Article and Find Full Text PDFInorg Chem
December 2024
Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Facultad de Ciencias, Universidad de Zaragoza - CSIC, 50009 Zaragoza, Spain.
An active catalytic system for the cross-dehydrogenative coupling (CDC) of a wide range of secondary amines with silanes is reported. The iridium(III) derivatives [Ir(H)(X)(κ-NSi)(L)] (NSi = {4,8-dimethylquinoline-2-yloxy}dimethylsilyl; L = coe, X = Cl, ; L = coe, X = OTf, ; L = PCy, X = Cl, ; L = PCy X = OTf, ), which are stabilized by a weak yet noticeable Ir···H-C agostic interaction between the iridium and one of the C-H bonds of the 8-Me substituent of the NSi ligand, have been prepared and fully characterized. These species have proven to be effective catalysts for the CDC of secondary amines with hydrosilanes.
View Article and Find Full Text PDFChempluschem
November 2024
Institute of Chemical Engineering, Ural Federal University, 19 Mira Str., 620062, Ekaterinburg, Russian Federation.
Azoloazine derivatives are known as promising small molecules that are potentially able to counteract a broad spectrum of RNA viruses including SARS-CoV-2. However, a pool of synthetic pathways to provide convenient structural modification of such compounds without de novo construction of the heterocyclic scaffold is rather limited so far. This work proposes an approach to the direct C(sp)-H functionalization of azolopyrimidine substrates with aromatic thiol residues, mediated by the iodine/persulfate reagent system.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Department of Chemistry, Technical University of Denmark, 2800 Kgs., Lyngby, Denmark.
Alkyl phosphonates are important motifs in medicinal chemistry, yet their efficient synthesis by direct C(sp)-H functionalization remains a challenge. Here, we report straightforward access to benzylic phosphonates by direct C(sp)-H functionalization in a cross-dehydrogenative-coupling reaction between non-specialized alkylarenes and unfunctionalized phosphites. Notably, the C-H substrates are used as the limiting reagents.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China.
Asymmetric catalytic versions of electricity-driven processes hold immense potential for the sustainable preparation of chiral compounds. However, the involvement of anodic oxidative cross-dehydrogenative coupling events between two distinct nucleophiles makes it challenging for a chiral catalyst to regulate the stereochemistry of the products. Our current electrocatalytic strategy for enantioconvergent cross-dehydrogenative α- and γ-nitroalkylation via radical-based pathways produces an array of enantioenriched nitroesters without supplementary stoichiometric oxidants.
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