A protocol for the mechanochemical synthesis of copper(I)/N-heterocyclic carbene complexes using cheap and readily available KPO as base has been developed. This method employing a ball mill is amenable to typical simple copper(I)/NHC complexes but also to a sophisticated copper(I)/N-heterocyclic carbene complex bearing a guanidine moiety. In this way, the present approach circumvents commonly employed silver(I) complexes which are associated with significant and undesired waste formation and the excessive use of solvents. The resulting bifunctional catalyst has been shown to be active in a variety of reduction/hydrogenation transformations employing dihydrogen as terminal reducing agent.
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http://dx.doi.org/10.3762/bjoc.19.34 | DOI Listing |
Chempluschem
November 2024
Department of Chemical Sciences, Indian Institute of Science Education and Research Berhampur, Transit Campus, Industrial Training Institute (ITI), Engineering School Road, Ganjam, Odisha, 760010, India.
Reactions of bipyridyl-functionalized imidazole-thiones and selones with MeX (X=I, OTf) afforded sulfenyl and selenenyl cations [(NNC)EMe]X (2/3, E=S, Se). Further reactions of these main-group cations with [Cu(CHCN)]BF, Cu(OTf) furnished dicationic [{Cu(μ-I)(NNC)EMe}][Y] (5/6, Y=BF, OTf) and tricationic copper(I) complexes [Cu{(NNC)EMe}](OTf)BF (7 a/7 b) when employed [(NNC)EMe]I and [(NNC)EMe]OTf respectively. All these cationic complexes were characterized by various spectroscopic techniques, including X-ray diffraction analysis.
View Article and Find Full Text PDFChemistry
November 2024
Department of Oils, Oleochemicals and Surfactants Technology, Institute of Chemical Technology, N. P. Marg, Matunga, Mumbai, 400019, India.
Photoswitchable (pre)catalysts, N,N'-bis-azobenzene-based (NHC)gold(I) and N,N'-bis-azobenzene-derived (NHC)copper(I) complexes are reported. Trans to cis isomerization of the attached photoswitchable moieties in the Au(I) complex enables four-fold decrement in the rate of oxazoline formation reaction. Whereas the progress of the copper(I) catalyzed, azide-alkyne cycloaddition reaction gets reduced by at least threefold.
View Article and Find Full Text PDFDalton Trans
July 2024
Technical University of Munich, Campus Straubing for Biotechnology and Sustainability, Chair of Biogenic Functional Materials, Schulgasse 22, 94315 Straubing, Germany.
J Org Chem
July 2024
School of Chemical Sciences, National Institute of Science Education and Research (NISER), Bhubaneswar, Odisha 752050, India.
In this work, we have developed an efficient method for the intramolecular double hydroamination of aniline by employing -amino 1,6-diyne as a potential starting material. This protocol enables easy access to bioactive motif 3,4-dihydro-1-[1,4]oxazino[4,3-]indole through an intramolecular cascade bicyclization and concomitant isomerization pathway in one pot. This transformation has been effectively achieved by utilizing a stereoelectronically tuned, π-accepting NHC-supported copper(I) system.
View Article and Find Full Text PDFDalton Trans
February 2024
Department of Chemistry, University of Bath, Bath, BA2 7AY, UK.
Liquid assisted ball milling of [NHC]HBr (NHC = N-heterocyclic carbene) salts with copper(I) chloride, and a range of alkali metal complexes was shown to efficiently produce (NHC)CuX (NHC = normal or RE-NHC, X = halide, alkoxide, amide, alkyl, aryl; RE-NHC = ring-expanded NHC).
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