The effective catalytic N-methylation of anilines using CO2 as C1 source and molecular hydrogen reducing agent was demonstrated the well-defined [Ru(triphos)(tmm)] catalyst. Secondary primary (shown) aromatic amines were mono- or dialkylated, respectively, in high yields. amides coupled with amide hydrogenation offers an efficient approach to unsymmetrical tertiary methyl/alkyl/aromatic amines. As a service our authors readers, this journal provides supporting information supplied by...

Abstract Dieser Aufsatz diskutiert die Chancen und Herausforderungen für Nutzung der Kombination aus Kohlendioxid Wasserstoff als C 1 ‐Synthon in katalytischen Reaktionen Prozessen. Die Transformationen werden anhand des Reduktionsgrades Bindungsknüpfung geordnet, wobei chemische Wertschöpfungskette von großvolumigen Grundchemikalien bis hin zu komplexen Molekülen mit biologischer Wirkung abgedeckt wird. chemischen erlauben zum einen Speicherung erneuerbaren Energien stofflichen Produkten...

Abstract The use of the well‐defined [Ru(triphos)(tmm)] catalyst, CO 2 as C 1 source, and H reducing agent enabled reductive methylation isolated imines, well direct coupling amines with aldehydes subsequent in situ formed imines. method, which afforded corresponding N‐methyl very good to excellent yields, was also used for preparation antifungal butenafine one step no apparent waste, thus increasing atom efficiency its synthesis.

Abstract The synthesis of dimethoxymethane (DMM) by a multistep reaction methanol with carbon dioxide and molecular hydrogen is reported. Using the catalyst [Ru(triphos)(tmm)] in combination Lewis acid Al(OTf) 3 resulted versatile catalytic system for various dialkoxymethane ethers. This new provides first synthetic example selective conversion into formaldehyde oxidation level, thus opening access to structures using this important C 1 source.

[Ru(triphos)(tmm)] wurde in der katalytischen N-Methylierung von Anilinen eingesetzt unter Verwendung CO2 als C1-Quelle und molekularem Wasserstoff Reduktionsmittel. Sekundäre primäre aromatische Amine wurden hohen Ausbeuten mono- bzw. dialkyliert. In Kombination mit Amidhydrierung bietet die Amiden einen effizienten Zugang zu nichtsymmetrischen tertiären Methyl-/Alkyl-/aromatischen Aminen.

Abstract The industrial production of polymeric materials is continuously increasing, but sustainable concepts directing towards a circular economy remain rather elusive. present investigation focuses on the recycling polyoxymethylene polymers, facilitated through combined catalytic processing polymer waste and biomass‐derived diols. integrated concept enables value‐added cyclic acetals, which can flexibly function as solvents, fuel additives, pharmaceutical intermediates, even monomeric for...

Abstract Some ethers, such as cyclopentyl methyl ether and di‐ n ‐butyl ether, which can be considered “greener” solvents than N , ‐dimethylacetamide (DMAc) or DMF, advantageously employed for the palladium‐catalyzed direct arylation of heteroaromatics. In presence ethers only 0.5–1 mol % palladium catalysts at 125–150 °C, 5‐arylation thiazoles, thiophenes, furans by using aryl bromides coupling partners proceeds in moderate to high yields.

Palladium-catalysed direct 5-arylation of metallated thiophenes fac-Ir(N^C(3')-thpy)(3) with aryl bromides via C-H bond functionalisation allows the synthesis a variety new Ir complexes in only one step (thpyH = 2,2'-thienylpyridine). The method offers simple modification nature ligand and hence photophysical properties such complexes.

Abstract The palladium‐catalyzed direct arylation of furans or thiophenes that contained secondary carboxamides at the C2 position proceeded regioselectively either C3 C5 positions, depending on reaction conditions. nature base was crucial for controlling regioselectivity reaction. We had previously observed that, in presence potassium acetate, favored. Herein, we report use cesium carbonate as and xylene solvent selectively afforded C3‐arylated thiophenes. reactivity furan‐2‐carboxamides...

Abstract The use of the well‐defined [Ru(triphos)(tmm)] catalyst, CO 2 as C 1 source, and H reducing agent enabled reductive methylation isolated imines, well direct coupling amines with aldehydes subsequent in situ formed imines. method, which afforded corresponding N‐methyl very good to excellent yields, was also used for preparation antifungal butenafine one step no apparent waste, thus increasing atom efficiency its synthesis.

Abstract The synthesis of trimethylamine (TMA) through a multicomponent combination ammonia with carbon dioxide and molecular hydrogen by using homogeneous ruthenium catalyst was explored. use [Ru(triphos)(tmm)] [triphos: 1,1,1‐tris(diphenylphosphinomethyl)ethane, tmm: trimethylene methane] together aluminum trifluoromethanesulfonate as co‐catalyst resulted in high conversion excellent selectivity for TMA organic solvents. Aqueous solutions ammonium chloride were methylated almost...

Abstract The synthesis of dimethoxymethane (DMM) by a multistep reaction methanol with carbon dioxide and molecular hydrogen is reported. Using the catalyst [Ru(triphos)(tmm)] in combination Lewis acid Al(OTf) 3 resulted versatile catalytic system for various dialkoxymethane ethers. This new provides first synthetic example selective conversion into formaldehyde oxidation level, thus opening access to structures using this important C 1 source.

Abstract Herein a transition‐metal catalyst system for the selective synthesis of cyclic and linear acetals from combined utilization carbon dioxide, molecular hydrogen, biomass derived diols is presented. Detailed investigations on substrate scope enabled selectivity reaction to be largely guided demonstrated possibility integrating broad variety molecules. This approach allowed change between favored formation acetals, originating bridging two with carbon‐dioxide based methylene unit. new...

Abstract To reduce the NO x and soot emissions of conventional diesel fuels, different renewable alternatives are investigated. One example oxymethylene ethers (OME ) chain lengths, which intended to be used as blends. Especially OME 3–5 show properties comparable diesel. The key producing longer OMEs is 1 feedstock, can react with formaldehyde afford larger molecules. This article reviews synthesis routes for , in order elucidate energy‐efficient methods.

The palladium-catalysed direct heteroarylation of the pyridyl-containing substrates, 2-(5-bromothiophen-2-yl)pyridine and 8-bromoquinoline, proceeds in moderate to high yields with a variety heteroarenes presence 1–2 mol% palladium catalyst. This approach allows access polyheteroaromatics which are interesting building blocks as (N⁁C)-chelate ligands. reaction regioselectively at C5 position thiophenes, thiazoles, furans or pyrroles tolerates various substituents such formyl, acetyl, ester,...

A novel and efficient palladium-catalysed direct di-heteroarylation of 1,2-dichloroperfluorocyclopentene with a variety heteroarenes is reported, giving rise to 1,2-di(heteroaryl)ylperfluorocyclopentene photochromic compounds. The reaction proceeds thiazoles, thiophenes or furan derivatives tolerates various substituents.

We report the palladium-catalyzed direct 5-arylation of both metalated and nonmetalated thiophene moieties iridium complexes 2, 3, 4 with aryl halides via C–H bond functionalization. This method opens new routes to varieties Ir in only one step, allowing easy modification nature ligand. The photophysical properties functionalized have been studied by means absorption emission spectroscopy. extension π-conjugated system induces a bathochromic hyperchromic shift spectra, an effect reproduced...

Abstract The sequential imination and intramolecular palladium‐catalyzed direct arylation of thiophene‐3‐carbaldehyde or furan‐3‐carbaldehyde with 2‐haloanilines provided a one‐pot access to furo‐ thienoquinolines in high yields H 2 O HBr as the major waste. Both electron‐withdrawing ‐donating substituents on 2‐haloaniline derivatives were tolerated. These thienoquinoline can be employed at C‐5 furyl thienyl moiety, variety corresponding products obtained yields.

The palladium-catalysed direct arylation of dithienylperfluorocyclopentene (DTE) derivatives proceeds in moderate to high yields with a variety aryl bromides the presence 5 mol% Pd(OAc)2/dppb as catalyst, and KOAc base. use cyclopentyl methyl ether solvent was found be crucial avoid decomposition reactants products. reaction regioselectively at C5 thiophenes, tolerates various substituents such formyl, acetyl, ester, nitrile or nitro on bromide. Therefore, this method allows straightforward...

Abstract The direct coupling of aryl halides with thiophene would be a considerable advantage for sustainable development because only HBr associated base as by-product is formed and the number steps to prepare these compounds less than in more classical reactions. We observed that through use 0.2 mol% Pd(OAc)2 catalyst, range bromides undergoes via C-H bond activation/functionalization reaction give 2-arylated thiophenes good yields. In most cases, traces polyarylated were detected when...

Selective elimination from 1,3-dienic allylic carbonates occurs in the presence of a catalytic amount [Ru(C(5)Me(5))(4,4'-di-Bu(t)-2,2'-bipyridine)(CH(3)CN)]PF(6) and provides efficient access to variety [3]dendralenes.

The palladium catalysed polyheteroarylation of benzene, biphenyl, fluorene, naphthalene or antracene derivatives via C–H bond functionalisation allows the synthesis a wide variety functionalised conjugated poly(hetero)aromatics in only one step. This simple method provides powerful tool to material chemists allowing tune easily physical properties materials.

Abstract Dialkoxymethanes are becoming increasingly important as fuel additives, formaldehyde surrogates, and chemical intermediates, but the effective synthesis remains challenging. Herein, catalytic of dialkoxymethane products using a molecular catalyst is reported. The system, comprising [Ru(triphos)(tmm)] in combination with Lewis acid Al(OTf) 3 , enables direct formic C1 building block high to excellent turnover numbers.