Metalated arylmethylisonitriles readily add to 2-chloropyridines to afford imidazo[1,5-a]pyridines. Analogous additions to imidoyl chlorides and a chloroquinoline provide imidazoles and an imidazo[1,5-a]quinolone which, like imidazo[1,5-a]pyridines, are valuable heterocycles for pharmaceutical synthesis.
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http://dx.doi.org/10.1039/c5cc08724d | DOI Listing |
Dalton Trans
January 2025
Division of Chemical and Biological Sciences, Ames National Laboratory, Ames, IA 50011, USA.
(PhPNP)Ru(H)(Cl)(CO) serves as a precatalyst to a variety of important catalytic transformations but most improvements have been restricted to the replacement of the CO ligand to the hydride or changing the Ph groups of the pincer for other aryl or alkyl groups. The ligand to the hydride is often another hydride and studies that utilize other ligands in catalysis are limited. In this work, we synthesized a series of [(PhPNP)Ru(H)(CO)(L)][BPh] complexes bearing isonitrile, PMe, or a N-heterocyclic ligand to the Ru-H.
View Article and Find Full Text PDFOrg Lett
January 2025
Organic Chemistry Department, Faculty of Science, Autonomous University of Madrid, 28049 Madrid, Spain.
The functionalization of the C-N bond of amines is a straightforward strategy for the construction of complex scaffolds or for the late-stage functionalization of pharmaceuticals. Herein, we describe a photoredox-catalyzed strategy for the deaminative alkylation of primary amine-derived isonitriles that provides unnatural amino acid derivatives under mild conditions. The use of silacarboxylic acids as silyl radical precursors enables the generation of carbon-centered radicals that allow the construction of Csp-Csp bonds via a Giese-type addition, avoiding the undesired hydrodeamination product.
View Article and Find Full Text PDFACS Catal
December 2024
Organic Chemistry Department and Center for Innovation in Advanced Chemistry (ORFEO-CINQA), Universidad Autónoma de Madrid (UAM), 28049 Madrid, Spain.
Herein, we demonstrate the ability of isonitriles to be used as alkyl radical precursors in a photoredox-catalyzed transformation involving selective C-N cleavage and Csp-Csp bond formation. This protocol allows for the preparation of functionalized heteroarenes from readily available isonitriles through a decyanation process. The reaction is general for primary, secondary, and tertiary substrates, including amino acid derivatives and druglike molecules.
View Article and Find Full Text PDFOrg Lett
December 2024
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Chemistry and Chemical Engineering, Center for Advanced Low-Dimension Materials, Donghua University, Shanghai 201620, China.
We report a radical cyano-cyclization of 1,6-enynes with isonitriles via photochemically driven nickel catalysis, forging alkenyl nitrile-tethered γ-lactams under mild conditions. This reaction leverages the photoexcitation of generated nickel (isonitrile) species to facilitate isonitriles serving as alkyl radical precursors and cyanide sources. The reaction accommodates a wide range of substrates, exhibiting excellent regioselectivity and / stereoselectivity.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Chemistry and Chemical Engineering, Center for Advanced Low-Dimension Materials, Donghua University, Shanghai 201620, China.
The exploration of strong chemical bonds as synthetic handles offers new disconnection strategies for the synthesis of functionalized molecules via transition metal catalysis. However, the slow oxidative addition rate of these covalent bonds to a transition metal center hampers their synthetic utility. Here, we report a C(sp)-N bond activation strategy that bypasses thermodynamically challenging 2e or 1e oxidative addition via a distinct pathway in nickel catalysis.
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