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A Stable Manganese Pincer Catalyst for the Selective Dehydrogenation of Methanol
For the first time, structurally defined manganese pincer complexes catalyze the dehydrogenation of aqueous methanol to hydrogen and carbon dioxide, which is a transformation of interest with regard to the implementation of a hydrogen and methanol economy. Excellent long-term stability was demonstrated for the Mn-PNPiPr catalyst, as a turnover of more than 20 000 was reached. In addition to methanol, other important hydrogen carriers were also successfully dehydrogenated.
Unprecedented selective homogeneous cobalt-catalysed reductive alkoxylation of cyclic imides under mild conditions
The first general and efficient non-noble metal-catalysed reductive C2-alkoxylation of cyclic imides (phthalimides and succinimides) is presented. Crucial for the success is the use of [Co(BF4)2·6H2O/triphos (L1)] combination and no external additives are required. Using the optimal cobalt-system, the hydrogenation of the aromatic ring of the parent phthalimide is avoided and only one of the carbonyl groups is selectively functionalized. The resulting products, N- and aryl-ring substituted 3-alkoxy-2,3-dihydro-1H-isoindolin-1-one and N-substituted 3-alkoxy-pyrrolidin-2-one derivatives, are prepared under mild conditions in good to excellent isolated yields. Intramolecular reductive couplings can also be performed affording tricyclic compounds in a one-step process. The present protocol opens the way to the development of new base-metal processes for the straightforward synthesis of functionalized N-heterocyclic compounds of pharmaceutical and biological interest.
Towards a general ruthenium-catalyzed hydrogenation of secondary and tertiary amides to amines
A broad range of secondary and tertiary amides has been hydrogenated to the corresponding amines under mild conditions using an in situ catalyst generated by combining [Ru(acac)3], 1,1,1-tris(diphenylphosphinomethyl)ethane (Triphos) and Yb(OTf)3. The presence of the metal triflate allows to mitigate reaction conditions compared to previous reports thus improving yields and selectivities in the desired amines. The excellent isolated yields of two scale-up experiments corroborate the feasibility of the reaction protocol. Control experiments indicate that, after the initial reduction of the amide carbonyl group, the reaction proceeds through the reductive amination of the alcohol with the amine arising from collapse of the intermediate hemiaminal.
Selective catalytic two-step process for ethylene glycol from carbon monoxide
Upgrading C1 chemicals (for example, CO, CO/H2, MeOH and CO2) with C-C bond formation is essential for the synthesis of bulk chemicals. In general, these industrially important processes (for example, Fischer Tropsch) proceed at drastic reaction conditions (>250 °C; high pressure) and suffer from low selectivity, which makes high capital investment necessary and requires additional purifications. Here, a different strategy for the preparation of ethylene glycol (EG) via initial oxidative coupling and subsequent reduction is presented. Separating coupling and reduction steps allows for a completely selective formation of EG (99%) from CO. This two-step catalytic procedure makes use of a Pd-catalysed oxycarbonylation of amines to oxamides at room temperature (RT) and subsequent Ru- or Fe-catalysed hydrogenation to EG. Notably, in the first step the required amines can be efficiently reused. The presented stepwise oxamide-mediated coupling provides the basis for a new strategy for selective upgrading of C1 chemicals.
Synthesis of Single Atom Based Heterogeneous Platinum Catalysts: High Selectivity and Activity for Hydrosilylation Reactions
Catalytic hydrosilylation represents a straightforward and atom-efficient methodology for the creation of C-Si bonds. In general, the application of homogeneous platinum complexes prevails in industry and academia. Herein, we describe the first heterogeneous single atom catalysts (SACs), which are conveniently prepared by decorating alumina nanorods with platinum atoms. The resulting stable material efficiently catalyzes hydrosilylation of industrially relevant olefins with high TON (≈105). A variety of substrates is selectively hydrosilylated including compounds with sensitive reducible and other functional groups (N, B, F, Cl). The single atom based catalyst shows significantly higher activity compared to related Pt nanoparticles.
Efficient and selective hydrogenation of amides to alcohols and amines using a well-defined manganese-PNN pincer complex
Novel well-defined NNP and PNP manganese pincer complexes have been synthetized and fully characterized. The catalyst Mn-2 containing an imidazolyaminolphosphino ligand shows high activity and selectivity in the hydrogenation of a wide range of secondary and tertiary amides to the corresponding alcohols and amines, under relatively mild conditions. For the first time, more challenging substrates like primary aromatic amides including an actual herbicide can also be hydrogenated using this earth-abundant metal-based pincer catalyst.
A robust iron catalyst for the selective hydrogenation of substituted (iso)quinolones
By applying N-doped carbon modified iron-based catalysts, the controlled hydrogenation of N-heteroarenes, especially (iso)quinolones, is achieved. Crucial for activity is the catalyst preparation by pyrolysis of a carbon-impregnated composite, obtained from iron(ii) acetate and N-aryliminopyridines. As demonstrated by TEM, XRD, XPS and Raman spectroscopy, the synthesized material is composed of Fe(0), Fe3C and FeNx in a N-doped carbon matrix. The decent catalytic activity of this robust and easily recyclable Fe-material allowed for the selective hydrogenation of various (iso)quinoline derivatives, even in the presence of reducible functional groups, such as nitriles, halogens, esters and amides. For a proof-of-concept, this nanostructured catalyst was implemented in the multistep synthesis of natural products and pharmaceutical lead compounds as well as modification of photoluminescent materials. As such this methodology constitutes the first heterogeneous iron-catalyzed hydrogenation of substituted (iso)quinolones with synthetic importance.
Correction: A robust iron catalyst for the selective hydrogenation of substituted (iso)quinolones
The authors regret that the term “(iso)quinolones” was used throughout the article, including the title, when the correct term should be “(iso)quinolines”. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.
Cobalt-catalysed reductive C-H alkylation of indoles using carboxylic acids and molecular hydrogen
The direct CH-alkylation of indoles using carboxylic acids is presented for the first time. The catalytic system based on the combination of Co(acac)3 and 1,1,1-tris(diphenylphosphinomethyl)-ethane (Triphos, L1), in the presence of Al(OTf)3 as co-catalyst, is able to perform the reductive alkylation of 2-methyl-1H-indole with a wide range of carboxylic acids. The utility of the protocol was further demonstrated through the C3 alkylation of several substituted indole derivatives using acetic, phenylacetic or diphenylacetic acids. In addition, a careful selection of the reaction conditions allowed to perform the selective C3 alkenylation of some indole derivatives. Moreover, the alkenylation of C2 position of 3-methyl-1H-indole was also possible. Control experiments indicate that the aldehyde, in situ formed from the carboxylic acid hydrogenation, plays a central role in the overall process. This new protocol enables the direct functionalization of indoles with readily available and stable carboxylic acids using a non-precious metal based catalyst and hydrogen as reductant.
Selective cobalt nanoparticles for catalytic transfer hydrogenation of N-heteroarenes
Nitrogen modified cobalt catalysts supported on carbon were prepared by pyrolysis of the mixture generated from cobalt(ii) acetate in aqueous solution of melamine or waste melamine resins, which are widely used as industrial polymers. The obtained nanostructured materials catalyze the transfer hydrogenation of N-heteroarenes with formic acid in the absence of base. The optimal Co/Melamine-2@C-700 catalyst exhibits high activity and selectivity for the dehydrogenation of formic acid into molecular hydrogen and carbon dioxide and allows for the reduction of diverse N-heteroarenes including substrates featuring sensitive functional groups.