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We demonstrate the participation of cobalt in a photoinduced ligand-to-metal charge transfer process, which leads to the formation of ligand-based radical species and enables both homo and hetero cross-dehydrogenative coupling of indoles with decent yield at room temperature. This photo-induced LMCT process is substantiated by a series of mechanistic investigations.

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A convenient and efficient transition-metal-free method has been developed for the C(sp)-H alkoxylation/aryloxylation of 1,4-quinones by direct cross-dehydrogenative coupling with readily available alcohols and phenols in the presence of TEMPO under simple and mild conditions. The method allowed the installation of a wide range of alkoxy/aryloxy groups, exhibited high functional group tolerance, showed a broad substrate scope, afforded good to excellent yields of products in a simple one-pot operation, and could be performed on a gram scale. Mechanistic investigation indicated the involvement of the radical pathway.

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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.

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Cross-Dehydrogenative Coupling of Secondary Amines with Silanes Catalyzed by Agostic Iridium-NSi Species.

Inorg Chem

January 2025

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.

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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.

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