scholarly journals Recent Advances in Copper Catalyzed Alcohol Oxidation in Homogeneous Medium

Molecules ◽  
2020 ◽  
Vol 25 (3) ◽  
pp. 748 ◽  
Author(s):  
Telma F. S. Silva ◽  
Luísa M. D. R. S. Martins

The development of sustainable processes and products through innovative catalytic materials and procedures that allow a better use of resources is undoubtedly one of the most significant issues facing researchers nowadays. Environmental and economically advanced catalytic processes for selective oxidation of alcohols are currently focused on designing new catalysts able to activate green oxidants (dioxygen or peroxides) and applying unconventional conditions of sustainable significance, like the use of microwave irradiation as an alternative energy source. This short review aims to provide an overview of the recently (2015–2020) discovered homogeneous aerobic and peroxidative oxidations of primary and secondary alcohols catalyzed by copper complexes, highlighting new catalysts with potential application in sustainable organic synthesis, with significance in academia and industry.

Nanomaterials ◽  
2020 ◽  
Vol 10 (11) ◽  
pp. 2111
Author(s):  
Inês A. S. Matias ◽  
Ana P. C. Ribeiro ◽  
Ana M. Ferraria ◽  
Ana M. Botelho do Rego ◽  
Luísa M. D. R. S. Martins

For the first time, herein is reported the use of a magnetic core-shell support for a C-scorpionate metallic complex. The prepared hybrid material, that consists on the C-scorpionate iron(II) complex [FeCl2{κ3-HC(pz)3}] (pz, pyrazolyl) immobilized at magnetic core-shell particles (Fe3O4/TiO2), was tested as catalyst for the oxidation of secondary alcohols using the model substrate 1-phenylethanol. Moreover, the application of alternative energy sources (e.g., ultrasounds, microwaves, mechanical or thermal) for the peroxidative alcohol oxidation using the magnetic heterogenized iron(II) scorpionate led to different/unusual outcomes that are presented and discussed.


2018 ◽  
Vol 4 (1) ◽  
pp. 27-30 ◽  
Author(s):  
Olena Savchenko ◽  
◽  
Vasyl Zhelykh ◽  
Yurii Yurkevych ◽  
Khrystyna Kozak ◽  
...  

Catalysts ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 26
Author(s):  
Ivan Bassanini ◽  
Erica Elisa Ferrandi ◽  
Sergio Riva ◽  
Daniela Monti

Laccases are multicopper oxidases, which have been widely investigated in recent decades thanks to their ability to oxidize organic substrates to the corresponding radicals while producing water at the expense of molecular oxygen. Besides their successful (bio)technological applications, for example, in textile, petrochemical, and detoxifications/bioremediations industrial processes, their synthetic potentialities for the mild and green preparation or selective modification of fine chemicals are of outstanding value in biocatalyzed organic synthesis. Accordingly, this review is focused on reporting and rationalizing some of the most recent and interesting synthetic exploitations of laccases. Applications of the so-called laccase-mediator system (LMS) for alcohol oxidation are discussed with a focus on carbohydrate chemistry and natural products modification as well as on bio- and chemo-integrated processes. The laccase-catalyzed Csp2-H bonds activation via monoelectronic oxidation is also discussed by reporting examples of enzymatic C-C and C-O radical homo- and hetero-couplings, as well as of aromatic nucleophilic substitutions of hydroquinones or quinoids. Finally, the laccase-initiated domino/cascade synthesis of valuable aromatic (hetero)cycles, elegant strategies widely documented in the literature across more than three decades, is also presented.


Energies ◽  
2021 ◽  
Vol 14 (10) ◽  
pp. 2948
Author(s):  
Soufia Mohammadi ◽  
Pilar Monsalvete Álvarez de Uribarri ◽  
Ursula Eicker

Biogas technology is an important alternative energy source worldwide. Blackwater and kitchen refuse represent ideal waste streams for bioenergy recovery through anaerobic co-digestion. Modeling of the biokinetics of anaerobic digestion on several aspects, such as microbial activity, substrate degradation, and methane production, from co-digestion of black water (BW) and kitchen refuse (KR) was the objective of this research. A mathematical model was developed towards a simulation based on mass balances on biomass, the organic substrate, and biogas. The model was implemented in INSEL and experimental data from the literature were used for model validation. The study shows that the simulation results fit well with the experimental data. The energy consumption and generation potential of anaerobic co-digestion of BW and KR were calculated to investigate if the produced biogas could supply the digester’s energy demand. This study can be used to pre-design anaerobic digestion systems in eco-districts.


Synlett ◽  
2018 ◽  
Vol 29 (18) ◽  
pp. 2404-2407 ◽  
Author(s):  
Tsunehisa Hirashita ◽  
Yuto Sugihara ◽  
Shota Ishikawa ◽  
Yohei Naito ◽  
Yuta Matsukawa ◽  
...  

Sodium hypochlorite pentahydrate (NaOCl·5H2O) is capable of oxidizing alcohols in acetonitrile at 20 °C without the use of catalysts. The oxidation is selective to allylic, benzylic, and secondary alcohols. ­Aliphatic primary alcohols are not oxidized.


1999 ◽  
Vol 77 (3) ◽  
pp. 308-312 ◽  
Author(s):  
Alfons L Baumstark ◽  
Franci Kovac ◽  
Pedro C Vasquez

The oxidation of several series of secondary alcohols 2-9, ethers 10-17, and related derivatives 18 and19, by dimethyldioxirane, 1, in acetone at 25°C produced the corresponding ketones in good to excellent yields for all but two cases. (The exceptions: oxidation of 1-methoxy-2-methyl-1-phenylpropane (48%) and 1-methoxy-2,2-dimethyl-1-phenylpropane (24%).) The oxidation of the secondary alcohols was found to yield k2 values that were roughly 10-fold greater than those of the corresponding methyl ethers. The rate constant for oxidation of a silyl ether was slightly lower than that for the corresponding methyl ether while that for the ester derivative was roughly half the value. For oxidation of alcohols and methyl ethers, the k2 values became smaller as the R " series (Me, Et, nPr, iPr, and tBu) increased in steric bulk (ρ* = 1.7; r = 0.998 and ρ* = 3.2; r = 0.95, respectively). The Hammett study for the oxidation of the methyl ethers of α-methyl-p-benzyl alcohols (10, 20-25) yielded a ρ value of -0.74. The activation parameters for oxidation of the parent compound of the ether series (1-methoxy-1-phenylethane) were ΔH‡ = 14.8 ± 0.5 kcal/mol, ΔS‡ = -21.9 eu, ΔG‡ = 21.3 kcal/mol, k2 (25°C) = 1.6 × 10-3 M-1 s-1. The mechanistic aspects of the oxidation are discussed in relation to two mechanistic extremes: (a) direct insertion of the oxygen atom into the C—H bond and (b) direct abstraction of the H by dimethyldioxirane to yield a caged-radical pair, with subsequent coupling to hemi-ketal intermediates that fragment to yield acetone, alcohol or water, and ketone as the final products.Key words: dimethyldioxirane, oxidation.


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