Ionic liquid (1-ethyl-3-methylimidazolium acetate, [C2C1im][AcO])-copper(ii) diacetate monohydrate-water-air (O2) systems have been investigated by (13)C NMR, EPR, spectrophotometry, HPLC, and synthetic chemistry methods at different temperatures. The C-H bond activation of [C2C1im](+) with the formation of the unusual dication 1,1'-diethyl-3,3'-dimethyl-2,2'-biimidazolium ([(C2C1im)2](2+)) at 50 °C and 1-ethyl-3-methyl-1H-imidazol-2(3H)-one (C2C1imO) at 50-85 °C was revealed. Two new complexes with the above compounds, [(C2C1im)2][Cu(AcO)4] and Cu2(AcO)4(C2C1imO)2, were isolated from the systems and characterized by X-ray structural analysis. Catalytic cycles with the participation of copper(ii) acetate and dioxygen and the production of [(C2C1im)2](2+) and C2C1imO have been proposed. The catalysis presumably includes the formation of the Cu(II)(O2)Cu(II) active centre with μ-η(2):η(2)-peroxide bridging in analogy with tyrosinase and catechol oxidase activity.
The isoquinoline core is present in one of the largest subsets of bioactive natural products. The multifunctional isoquinoline core exerts diverse bioactivity, resulting in the development of numerous isoquinoline-based drugs and molecules that are currently under clinical trials. We developed a new approach for phosphite-mediated [1,2] alkyl migration for an overall -C-H alkylation -alkylation of isoquinoline.
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Jiangwan Campus, Fudan University, Shanghai 200438, China.
The phosphaguanidinate rare-earth-metal bis(aminobenzyl) complexes [(PhP)C(NCHPr-2,6)]Ln(CHCH NMe-) (Ln = Y(1-Y) and Lu(1-Lu)) were synthesized by the protonolysis of (PhP)[C(NHR)(NR)] (R = 2,6-(Pr)CH) with Ln(CHCHNMe-) (Ln = Y and Lu). Interestingly, the ring-opening rearrangement product [-MeNCHCHC(NCHPr-2,6)]Lu(CHCHNMe-)[O(CH)PPh] (2) was obtained when the acid-base reaction was carried out in THF solution at 60 °C for 36 h. Additionally, the trinuclear homometallic yttrium multimethyl/methylidene complex {[(PhP)C(NCHPr-2,6)]Y(μ-Me)}(μ-Me)(μ-CH) (3) was synthesized by the treatment of 1-Y with AlMe (2 equiv.
C-H bond activation is the first step in manufacturing chemical products from readily available light alkane feedstock and typically proceeds via carbon-intensive thermal processes. The ongoing emphasis on decarbonization via electrification motivates low-temperature electrochemical alternatives that could lead to sustainable chemicals production. Platinum (Pt) electrocatalysts have shown activity towards reacting alkanes; however, little is known about propane electrocatalytic activation and conditions suitable for enabling selective oxidation to valuable products.
Metal-Organic Frameworks (MOFs) are an emerging class of solid-state materials comprising inorganic elements and organic molecules. These hybrid materials are widely recognized for their diverse properties, rendering them indispensable in the field of organic synthesis, material science and the pharmaceutical industry. Although the traditional batch methods for MOFs synthesis are well-developed, they often struggle with reproducibility, scalability and environmental issues.
