1706-12-3Relevant articles and documents
Oxidation of m-Phenoxytoluene with Ceric Trifluoroacetate
Marrocco, Matt,Brilmyer, George
, p. 1487 - 1491 (1983)
Ceric trifluoroacetate in aqueous trifluoroacetic acid has been found to be especially effective for the oxidation of activated toluenes to the corresponding aldehydes.Ceric ion is consumed in stoichiometric amounts but can be regenerated electrochemically at high current efficiencies (95 percent).A detailed study of the oxidation of m-phenoxytoluene to m-phenoxybenzaldehyde is presented.A study of the reaction mechanism, which involves both cations and radical cations, led to a choise of cosolvents which stabilize these intermediates and thus increase the yield of aldehyde formation.
Using Data Science To Guide Aryl Bromide Substrate Scope Analysis in a Ni/Photoredox-Catalyzed Cross-Coupling with Acetals as Alcohol-Derived Radical Sources
Doyle, Abigail G.,Gandhi, Shivaani S.,Jiang, Shutian,Kariofillis, Stavros K.,Martinez Alvarado, Jesus I.,?urański, Andrzej M.
supporting information, p. 1045 - 1055 (2022/01/19)
Ni/photoredox catalysis has emerged as a powerful platform for C(sp2)–C(sp3) bond formation. While many of these methods typically employ aryl bromides as the C(sp2) coupling partner, a variety of aliphatic radical sources have been investigated. In principle, these reactions enable access to the same product scaffolds, but it can be hard to discern which method to employ because nonstandardized sets of aryl bromides are used in scope evaluation. Herein, we report a Ni/photoredox-catalyzed (deutero)methylation and alkylation of aryl halides where benzaldehyde di(alkyl) acetals serve as alcohol-derived radical sources. Reaction development, mechanistic studies, and late-stage derivatization of a biologically relevant aryl chloride, fenofibrate, are presented. Then, we describe the integration of data science techniques, including DFT featurization, dimensionality reduction, and hierarchical clustering, to delineate a diverse and succinct collection of aryl bromides that is representative of the chemical space of the substrate class. By superimposing scope examples from published Ni/photoredox methods on this same chemical space, we identify areas of sparse coverage and high versus low average yields, enabling comparisons between prior art and this new method. Additionally, we demonstrate that the systematically selected scope of aryl bromides can be used to quantify population-wide reactivity trends and reveal sources of possible functional group incompatibility with supervised machine learning.
Magnetization of graphene oxide nanosheets using nickel magnetic nanoparticles as a novel support for the fabrication of copper as a practical, selective, and reusable nanocatalyst in C-C and C-O coupling reactions
Hajjami, Maryam,Moradi, Parisa
, p. 25867 - 25879 (2021/08/09)
Catalyst species are an important class of materials in chemistry, industry, medicine, and biotechnology. Moreover, waste recycling is an important process in green chemistry and is economically efficient. Herein, magnetic graphene oxide was synthesized using nickel magnetic nanoparticles and further applied as a novel support for the fabrication of a copper catalyst. The catalytic activity of supported copper on magnetic graphene oxide (Cu-ninhydrin@GO-Ni MNPs) was investigated as a selective, practical, and reusable nanocatalyst in the synthesis of diaryl ethers and biphenyls. Some of the obtained products were identified by NMR spectroscopy. This nanocatalyst has been characterized by atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM), wavelength dispersive X-ray spectroscopy (WDX), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and vibrating sample magnetometer (VSM) techniques. The results obtained from SEM shown that this catalyst has a nanosheet structure. Also, XRD and FT-IR analysis show that the structure of graphene oxide and nickel magnetic nanoparticles is stable during the modification of the nanoparticles and synthesis of the catalyst. The VSM curve of the catalyst shows that this catalyst can be recovered using an external magnet; therefore, it can be reused several times without a significant loss of its catalytic efficiency. The heterogeneity and stability of this nanocatalyst during organic reactions was confirmed by the hot filtration test and AAS technique.
