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Developing a general approach for the functionalization of coordinating heteroaromatic amines with alcohol is challenging. Here, we designed an efficient protocol using a pincer-NHC carbene-based Mn(I) complex for the selective -alkylation of 2-aminoazole molecules with ethanol and methanol. This methodology is versatile and applicable to the coupling of a wide range of alcohols, including methanol, ethanol, aryl alcohols, and both acyclic and cyclic aliphatic alcohols, with various 2-aminoazoles, aminopyridine, and aminoquinoline derivatives, to provide diverse monoalkylated compounds in good to excellent yields.

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Aluminacyclopropene-phosphine complex: a carbene-exchange reagent.

Chem Sci

August 2025

Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS 118 Route de Narbonne F-31062 Toulouse France

N-heterocyclic carbenes (NHCs) are extensively used as auxiliary ligands or organocatalysts thanks to their remarkable stability. However, due to their high structural stability, applications involving skeletal modifications without losing the low-valent nature (carbene exchange reactions) remain extremely rare. We report here that aluminacyclopropene-phosphine complex 1 promotes original "carbene-to-carbene" transformations of stable carbenes.

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In this study, we report our recent findings on the synthesis and reactivity of a novel 1,2,3-triazolin-5-imine-type mesoionic imine-carbodiimide (MII-CDI) adduct. Unlike reported NHC-CDI adducts, formed by the reactions of N-heterocyclic carbene (NHC) with CDI, these zwitterionic compounds undergo a spontaneous 1,3-hydrogen shift (1,3-H shift), resulting in guanidine-type compounds. The mechanism of this 1,3-H shift has been investigated through quantum chemical calculations.

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A relay Rh(II)/Pd(0) dual-catalyzed three-component allylic alkylation of alcohols, α-diazo 1,3-diketones, and allyl reagents is successfully developed, which provides a highly chemoselective method for the one-pot synthesis of acyclic α-quaternary allylated β-keto-esters. Remarkably, this transformation includes difunctionalizations of ketene intermediates instead of metal-carbene intermediates. Our protocol is characterized by mild conditions, simple raw materials, and good to excellent yields.

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Enantioselective access to 3,3'-disubstituted oxindole derivatives by N-heterocyclic carbene catalysis.

Org Biomol Chem

June 2025

School of Chemistry and Chemical Engineering/State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003, China.

An effectively enantioselective and regioselective N-heterocyclic carbene-catalyzed oxidative spiroannulation of isatin-derived enals with 2,4-dioxoesters to directly synthesize spirooxindole δ-lactones was realized. Subsequently, upon treatment with methanol under reflux, spirooxindole δ-lactones were effectively converted into acyclic 3,3'-disubstituted oxindole derivatives bearing an all-carbon quaternary center that might have been obtained through a novel sequence of deesterification and decarbonylation paths. This approach was qualified with a broad substrate scope and mild reaction conditions, achieving moderate to excellent yield and enantioselectivity.

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