589-82-2Relevant articles and documents
Chelating alcohols accelerate the samarium diiodide mediated reduction of 3-heptanone
Dahlén, Anders,Hilmersson, G?ran
, p. 5565 - 5569 (2001)
Initial rate studies of samarium diiodide mediated reduction of 3-heptanone to 3-heptanol are reported. The reduction of 3-heptanone with the polydentate tri(ethylene glycol) methyl ether is 16 times faster than without a proton donor, and 4.3 times faster than methanol. The primary kinetic isotope effect (KIE) was measured as kH/kD ≈ 2, indicating a rate-determining proton transfer. Diols are superior to mono-alcohols as proton donors, the reduction of 3-heptanone is 255 times as fast with di(ethylene glycol) than in the absence of a proton donor. A mechanism of glycol accelerated samarium diiodide reduction is discussed.
Mechanistic Insights into the Aerobic Oxidation of Aldehydes: Evidence of Multiple Reaction Pathways during the Liquid Phase Oxidation of 2-Ethylhexanal
Vanoye, Laurent,Favre-Réguillon, Alain
, p. 335 - 346 (2022/02/10)
The liquid-phase aldehyde oxidation by molecular oxygen (autoxidation) has been known for about 2 centuries and is a critical organic transformation in both industrial applications and academic research. However, the general reaction pathway proposed for the aerobic oxidation of aldehydes into the corresponding carboxylic acid exhibits some inconstancies, in particular, for β-substituted aliphatic aldehydes. Thus, the liquid-phase aerobic oxidation of 2-ethylhexanal was further studied in acetonitrile at 20 °C with O2 at atmospheric pressure. By precisely monitoring the primary intermediate (peracid), product (carboxylic acid), and byproducts as a function of time and catalysts used, we demonstrated the pivotal role of the acylperoxy radical. The direct formation of peracid and carboxylic acid from the latter was highlighted by analyzing the composition of the reaction mixture at low conversion. Peracid could be converted into carboxylic acid by metal catalysts or through reaction workup. Consequently, the commonly accepted pathway of aerobic oxidation of aldehyde via a Criegee intermediate can be overlooked under these conditions.
Regioselective C-H hydroxylation of: N -alkanes using Shilov-type Pt catalysis in perfluorinated micro-emulsions
De Vos, Dirk E.,Janssen, Michiel
, p. 1264 - 1272 (2020/03/23)
Shilov-chemistry inspired catalysis has remained largely overlooked as a tool for establishing the remote hydroxylation of non-polar compounds, such as long linear alkanes, due to the need for an acidic aqueous solution. To circumvent the solubility issue, the concept of micellar catalysis is introduced, using PtII in perfluorinated micro-emulsions. Notably, the terminal C-H activation of n-heptane is demonstrated under an oxygen atmosphere using perfluorooctanoic acid (PFOA) as a surfactant, along with the intrinsic ability of PtII to convert the highly inert primary C-H bonds. Coordination of PtII to the carboxylate groups of PFOA proved to be particularly important for achieving maximum catalyst activity towards the hydrocarbon substrate solubilized inside the micelle interior. Based on these insights, optimization of the reaction parameters allowed a positional selectivity of 60% for 1-heptanol, among the C7 alcohols, to be achieved, using low catalyst and surfactant loadings under acid-free conditions.
Metal-Organic Architectures Assembled from Multifunctional Polycarboxylates: Hydrothermal Self-Assembly, Structures, and Catalytic Activity in Alkane Oxidation
Gu, Jinzhong,Wen, Min,Cai, Yan,Shi, Zifa,Arol, Aliaksandr S.,Kirillova, Marina V.,Kirillov, Alexander M.
, p. 2403 - 2412 (2019/02/28)
A three-component aqueous reaction system comprising copper(II) acetate (metal node), poly(carboxylic acid) with a phenylpyridine or biphenyl core (main building block), and 1,10-phenanthroline (crystallization mediator) was investigated under hydrothermal conditions. As a result, four new coordination compounds were self-assembled, namely, {[Cu(μ3-cpna)(phen)]·H2O}n (1), {[Cu(μ-Hbtc)(phen)]·H2O}n (2), {[Cu(μ3-Hcpic)(phen)]·2H2O}n (3), and [Cu6(μ-Hcptc)6(phen)6]·6H2O (4), where H2cpna = 5-(2′-carboxylphenyl)nicotinic acid, H3btc = biphenyl-2,4,4′-tricarboxylic acid, H3cpic = 4-(5-carboxypyridin-2-yl)isophthalic acid, H3cptc = 2-(4-carboxypyridin-3-yl)terephthalic acid, and phen = 1,10-phenanthroline. Crystal structures of compounds 1-3 reveal that they are 1D coordination polymers with a ladder, linear, or double-chain structure, while product 4 is a 0D hexanuclear complex. All of the structures are extended further [1D a?' 2D (1 and 2), 1D a?' 3D (3), and 0D a?' 3D (4)] into hydrogen-bonded networks. The type of a multicarboxylate building block has a considerable effect on the final structures of 1-4. The magnetic behavior and thermal stability of 1-4 were also investigated. Besides, these copper(II) derivatives efficiently catalyze the oxidation of cycloalkanes with hydrogen peroxide under mild conditions. The obtained products are the unique examples of copper derivatives that were assembled from H2cpna, H3btc, H3cpic, and H3cptc, thus opening up their use as multicarboxylate ligands toward the design of copper-organic architectures.
