Hierarchically porous N and S co-doped carbon was prepared by using 2,5-dihydroxy-1,4-benzoquinone as the carbon source, thiourea as the N and S source, and SiO2 particles as the template. Using the material as the catalyst, oxidative coupling of silanes with alcohols was conducted for the first time under metal-free conditions.

Hydration of internal aryl alkynes to provide aryl carbonyl compounds is a class of important reactions and has been widely investigated. However, the hydration of asymmetric internal aryl alkynes without directing groups usually gives an aryl ketone or a mixture of aryl ketone and α-aryl ketone. High regioselectivity to α-aryl ketone is a great challenge and has not been reported. Herein, we found that CuBr and p-fluoroaniline had an excellent synergistic effect in catalyzing the hydration of internal aryl alkynes without directing groups to α-aryl ketones with regioselectivity up to more than 90%, which is much greater than those reported. The reaction mechanism was proposed, and the reason for the high selectivity was clarified by a combination of density functional theory (DFT) calculation, condensed dual descriptor (CDD) study, and experimental results. It was demonstrated that the formations of α-aryl ketone and aryl ketone were promoted by different catalytic active species, CuBr and CuBr[p-fluoroaniline], respectively. CuBr enlarged the difference of electron population on the two triple-bond carbon atoms, resulting in α-aryl ketones as the main products.

N-methyl-tetrahydroquinolines (MTHQs) are a kind of very useful chemicals, which can be obtained from N-methylation of amines. However, the methylation of quinolines which is a kind of highly unsaturated nitrogen-containing heterocyclic aromatic compounds has not been reported. In this work, we report the first work for the synthesis of MTHQs by methylation of quinolines using CO2 and H2. It was found that Ru(acac)3-triphos [triphos: 1,1,1-tris(diphenylphosphinomethyl)ethanl] complex was very active and selective for the N-methylation reaction of quinolines, and the yield of the desired product could reach 99%.

Selective transformation of lignin into a valuable chemical, acetic acid, is possible. In their Communication on page 14868 ff. B. Han, H. Liu et al. propose a strategy for selective transformation of methoxy groups, which are abundant in lignin, into pure acetic acid. The conversions of methoxy groups in kraft lignin and organosolv lignin reached 87.3% and 80.4%, respectively, and no by-product was generated. This work opens the way to the production of pure chemicals by using lignin as the feedstock.

AbstractSelective transformation of lignin into a valuable chemical is of great importance and challenge owing to its complex structure. Herein, we propose a strategy for the transformation of methoxy group (-OCH3) which is abundant in lignin into pure highly valuable chemicals. As an example to apply this strategy, a route to produce acetic acid with high selectivity by conversion of methoxy group of lignin was developed. It was demonstrated that the methoxy group in lignin could react with CO and water to generate acetic acid over RhCl3 in the presence of a promoter. The conversions of methoxy group in the kraft lignin and organosolv lignin reached 87.5 % and 80.4 %, respectively, and no by-product was generated. This work opens the way to produce pure chemicals using lignin as the feedstock.

Die selektive Umwandlung von Lignin in Essigsäure ist das Thema der Zuschrift von B. Han, H. Liu et al. auf S. 15064. Mit einer von ihnen entwickelten Strategie überführen sie in Lignin zahlreich vorhandene Methoxygruppen in reine Essigsäure, wobei Umsätze von 87.3% und 80.4% für Kraft- bzw. Organosolv-Lignin erreicht werden und keine Nebenprodukte entstehen.

AbstractSelective transformation of lignin into a valuable chemical is of great importance and challenge owing to its complex structure. Herein, we propose a strategy for the transformation of methoxy group (-OCH3) which is abundant in lignin into pure highly valuable chemicals. As an example to apply this strategy, a route to produce acetic acid with high selectivity by conversion of methoxy group of lignin was developed. It was demonstrated that the methoxy group in lignin could react with CO and water to generate acetic acid over RhCl3 in the presence of a promoter. The conversions of methoxy group in the kraft lignin and organosolv lignin reached 87.5 % and 80.4 %, respectively, and no by-product was generated. This work opens the way to produce pure chemicals using lignin as the feedstock.

We carried out work on N-formylation of amines with CO2 and PhSiH3 to produce formamides catalyzed by a copper complex. It was found that the Cu(OAc)2–bis(diphenylphosphino)ethane (dppe) catalytic system was very efficient for these kind of reactions at room temperature and 1 atm CO2 with only 0.1 mol% catalyst loading.

In this work, we fabricated the poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized ruthenium(0) nanoclusters by reduction of RuCl3 using different reducing agents, and studied their catalytic activity in hydrogen generation from the decomposition of formic acid. It was demonstrated that N-vinyl-2-pyrrolidone (NVP), which is a monomer of PVP, could promote the reaction by coordination with Ru nanoparticles. The Ru nanoparticles catalyst reduced by sodium borohydride (NaBH4) exhibited highest catalytic activity for the decomposition of formic acid into H2 and CO2. The turnover of numenber (TOF) value could reach 26113 h–1 at 80 °C. We believe that the effective catalysts have potential of application in hydrogen storage by formic acid.