We herein report a two-step strategy for oxidative cleavage of lignin C–C bond to aromatic acids and phenols with molecular oxygen as oxidant. In the first step, lignin β-O-4 alcohol was oxidized to β-O-4 ketone over a VOSO4/TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl)] catalyst. In the second step, the C–C bond of β-O-4 linkages was selectively cleaved to acids and phenols by oxidation over a Cu/1,10-phenanthroline catalyst. Computational investigations suggested a copper-oxo-bridged dimer was the catalytically active site for hydrogen-abstraction from Cβ–H bond, which was the rate-determining step for the C–C bond cleavage.
Lignin in lignocellulosic biomass is the only renewable source for aromatic compounds, and effective valorization of lignin remains a significant challenge in biomass conversion processes. We have performed density functional theory calculations and experiments to investigate the cleavage mechanism of the C–O ether bond in the lignin model compound 2-phenoxy-1-phenylethanol with a β-O-4 linkage over a Pd(111) catalyst surface model. We propose the favorable reaction pathway to proceed as follows: the dilignol reactant gets dehydrogenated first on the α-carbon and then on the −OH group to generate its corresponding ketone 2-phenoxy-1-phenylethanone; the ketone continues to get dehydrogenated on the β-carbon by first a equilibrated keto–enol tautomerization to its enol form and then −OH dehydrogenation; the C–O ether bond cleavage happens afterward, leading to one-aromatic-ring surface intermediates followed by hydrogenation to yield acetophenone and phenol.
We present an experimental and computational study of the elementary steps of hydrazine hydrogen transfer on crystalline MoO2, and demonstrate its unique bifunctional metallic-basic properties in a catalytic hydrogenation reaction. Density functional theory (DFT) calculations suggest that the stepwise hydrogen transfer via the prior cleavage of the N–H bond rather than the N–N bond, is the key step to create the dissociated hydride and proton species on the dual Mo and O sites, marking its difference with common oxides. Crystalline MoO2 shows exceptionally high chemoselectivity toward the nitro reduction over C=C, C≡C, and C≡N groups at room temperature and lower, down to 0 °C, rendering it as a promising catalytic material for hydrogenation reactions.
Selective oxidative cleavage of a C-C bond offers a straightforward method to functionalize organic skeletons. Reported herein is the oxidative C-C bond cleavage of ketone for C-N bond formation over a cuprous oxide catalyst with molecular oxygen as the oxidant. A wide range of ketones and amines are converted into cyclic imides with moderate to excellent yields. In-depth studies show that both α-C-H and β-C-H bonds adjacent to the carbonyl groups are indispensable for the C-C bond cleavage. DFT calculations indicate the reaction is initiated with the oxidation of the α-C-H bond. Amines lower the activation energy of the C-C bond cleavage, and thus promote the reaction. New insight into the C-C bond cleavage mechanism is presented.
Creation of substrate-accessible interfacial defect sites will bring about new catalytic discoveries because substrate binding and activation on these sites are pivotal for controlling reaction intermediate and product selectivity. The partial oxidation of pristine Cu2O can lead to an excellent selective oxidation catalyst (CuO/Cu2O). The CuO/Cu2O, containing embedded CuO nanodomains on the surface and possessing abundant coordinatively unsaturated copper sites at the CuO-Cu2O interface, shows very high activity toward C-C bond cleavage and excellent selectivity toward formamides in trialkylamines oxidation. This result is exceptional because the previous works mainly offer dealkylated amines via C-N bond cleavage. The unusual catalysis by CuO/Cu2O is attributed to the co-activation of oxygen and amines in close proximity at the CuO-Cu2O interface. The present study contributes a new concept of delicate controlling substrate-accessible interfacial active sites on pristine oxide surfaces, and also offers a novel formamide synthesis method by trialkylamine oxidation.
Herein, we report CO2-mediated metathesis reactions between amines and DMF to synthesize formamides. More than 20 amines, including primary, secondary, aromatic, and heterocyclic amines, diamines, and amino acids, are converted to the corresponding formamides with good-to-excellent conversions and selectivities under mild conditions. This strategy employs CO2 as a mediator to activate the amine under metal-free conditions. The experimental data and in situ NMR and attenuated total reflectance IR spectroscopy measurements support the formation of the N-carbamic acid as an intermediate through the weak acid–base interaction between CO2 and the amine. The metathesis reaction is driven by the formation of a stable carbamate, and a reaction mechanism is proposed.
Heterogeneously catalyzed synthesis of quinazolinones or quinazolines is reported in this study. An α-MnO2 catalyst is found to be highly active and selective in the oxidative cyclization of anthranilamides or aminobenzylamines with alcohols using TBHP as an oxidant. This protocol exhibits a broad substrate scope, and is operationally simple without an additive.
We here report a new protocol for the formylation of various amines, primary or secondary, aromatic or alkyl, cyclic or linear, mono- or di-amine, with dimethylformamide (DMF) as the formylation reagent to obtain the corresponding formamides in good to excellent yields over CeO2 catalyst. The reaction requires no homogeneous acidic or basic additives and is tolerant to water.
Gold nanoparticles supported on ceria{110} crystal planes were more reactive than on ceria{111} and {100} in the oxidative dehydrogenation of alcohols. Kinetic analysis and a Hammett plot suggest that hydride transfer is involved, and the cationic gold is catalytically active.
Ceria showed excellent catalytic activity in the hydrolysis of 4-methyl-1,3-dioxane to 1,3-butanediol in 95% yield and in the one-pot synthesis of 1,3-butanediol from propylene and formaldehyde via Prins condensation and hydrolysis reactions in an overall yield of 60%. In-depth investigations revealed that ceria is a water-tolerant Lewis acid catalyst, which has seldom been reported previously. The ceria catalysts showed rather unusual high activity in hydrolysis, with a turnover number (TON) of 260. Our conclusion that ceria functions as a Lewis acid catalyst in hydrolysis reactions is firmly supported by thorough characterizations with IR and Raman spectroscopy, acidity measurements with IR and 31P magic-angle-spinning NMR spectroscopy, Na+/H+ exchange tests, analyses using the in situ active-site capping method, and isotope-labeling studies. A relationship between surface vacancy sites and catalytic activity has been established. CeO2(111) has been confirmed to be the catalytically active crystalline facet for hydrolysis. Water has been found to be associatively adsorbed on oxygen vacancy sites with medium strength, which does not lead to water dissociation to form stable hydroxides. 
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