Rhodium‐catalyzed hydroformylation of unsaturated fatty esters in aqueous media assisted by activated carbon
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Abstract Concerns about the environmental impact of chemical transformations prompted chemists to develop clean chemical processes using water as a solvent. Although appropriate for small partially water‐soluble molecules, these processes do not allow for the transformation of hydrophobic substrates due to the mass transfer limitation between the aqueous and the organic phase. In this context, we show that activated carbons can be used as mass transfer additives to promote the rhodium‐catalyzed hydroformylation of methyl oleate and other unsaturated olefins. Due to its mesoporous and hydrophobic character, the Nuchar®WV‐B activated carbon proved to be especially effective as mass transfer promoter. Actually, a significant increase in the conversion was observed. Additionally, more than 90% aldehydes were formed during the course of the reaction. When compared to other mass transfer promoters such as co‐solvents or cyclodextrins, Nuchar®WV‐B was by far the most efficient. Thus, the use of activated carbons appeared to be a suitable solution for the aqueous rhodium‐catalyzed hydroformylation of hydrophobic bio‐sourced substrates. Practical applications: The easiness with which the FAME hydroformylation could be implemented in water using activated carbons as mass transfer promoters is a major advantage in a context of an industrial–environmental approach. This finding is of importance as the obtained oxo‐products can be used in many industrial areas such as surfactants, polymers, or lubricants.Keywords:
Aqueous two-phase system
We report the formation of high-precision catalysts using encapsulated rhodium complexes. In the current example, the encapsulated rhodium catalyst shows unprecedented high selectivity in the rhodium-catalyzed hydroformylation of internal alkenes, forming predominantly one of the branched aldehydes. This catalyst system is the first example that is able to discriminate between carbon atoms C3 and C4 in trans-3-octene.
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The hydroformylation of olefins is one of the most important homogeneously catalyzed processes in industry to produce bulk chemicals. Despite the high catalytic activities and selectivity’s using rhodium-based homogeneous hydroformylation catalysts, catalyst recovery and recycling from the reaction mixture remain a challenging topic on a process level. Therefore, technical solutions involving alternate approaches with heterogeneous catalysts for the conversion of olefins into aldehydes have been considered and research activities have addressed the synthesis and development of heterogeneous rhodium-based hydroformylation catalysts. Different strategies were pursued by different groups of authors, such as the deposition of molecular rhodium complexes, metallic rhodium nanoparticles and single-atom catalysts on a solid support as well as rhodium complexes present in supported liquids. An overview of the recent developments made in the area of the heterogenization of homogeneous rhodium catalysts and their application in the hydroformylation of short-chain olefins is given. A special focus is laid on the mechanistic understanding of the heterogeneously catalyzed reactions at a molecular level in order to provide a guide for the future design of rhodium-based heterogeneous hydroformylation catalysts.
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Following the facile synthesis of a novel phosphine oxide compound, (diphenylphosphinoyl)phenylmethanol (1), this compound was employed as a ligand in the rhodium-catalyzed hydroformylation of alkenes, with good conversions and regioselectivities. This ligand was partially resolved using an enzyme, and enantioselective hydroformylation was carried out with the addition of a rhodium(I) complex. The rhodium(I) complex containing ligand 1 was not isolated, although it was subjected to low-temperature NMR studies.
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Carbonylation
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The present state of art on the application of carbene-rhodium complexes as stable catalysts for hydroformylation reaction is described. A critical analysis of the influence of pressure and temperature on the hydroformylation of non-modified rhodium complexes and those ones described in the presence of carbenes is also done. Finally, a set of experiments using NHCs prepared by us at different reactions conditions is presented and discussed. Keywords: Aliphatic olefins, hydroformylation, rhodium, N-heterocyclic carbene ligands, Rhodium-NHC Complexes, Rhodium-Carbonyl Complexes, Influence of pressure, styrene, Influence of Temperature
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1-Octene
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