Glycerol – A Non‐Innocent Solvent for Rh‐Catalysed Pauson–Khand Carbocyclisations

Chahdoura, Faouzi; Dubrulle, Laurent; Fourmy, Kévin; Durand, Jérôme; Madec, David; Gómez, Montserrat

doi:10.1002/ejic.201300651

Cited by 13 publications

(5 citation statements)

References 39 publications

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“…In solution, the electronic structure of Rh remains similar to the solid state, as found by XANES. According to the EXAFS data, the overall dimeric structure of [RhCl( 1 )] 2 is preserved in solution; however, one (or both) of the bridging chloro ligands are replaced by the solvent dioxane, which is in agreement with previous findings in Rh-catalyzed Pauson-Khand cyclizations . This observation agrees well with the commonly accepted catalytic cycle for Rh-diene-catalyzed asymmetric nucleophilic additions, g where the chloro-bridged dimeric Rh complex is first converted to the hydroxo-bridged dimeric Rh complex and then breaks down to the catalytically active monomeric diene Rh–OH species.…”

Section: Discussionmentioning

confidence: 99%

Experimental and Theoretical Study on the Role of Monomeric vs Dimeric Rhodium Oxazolidinone Norbornadiene Complexes in Catalytic Asymmetric 1,2- and 1,4-Additions

et al. 2020

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The influence of nuclearity and charge of chiral Rh diene complexes on the activity and enantioselectivity in catalytic asymmetric 1,2-additions of organoboron reagents to Ntosylimines and 1,4-additions to enones was investigated. For this purpose, cationic dimeric Rh(I) complex [(Rh(1)) 2 Cl]SbF 6 and cationic monomeric Rh(I) complex [RhOH 2 (2)]SbF 6 were synthesized from oxazolidinone-substituted 3-phenylnorbornadiene ligands 1 and 2, which differ in the substitution pattern at oxazolidinone C-5′ (CMe 2 vs CH 2 ) and compared with the corresponding neutral dimeric and monomeric Rh(I) complexes [RhCl(1)] 2 and [RhCl(2)]. Structural, electronic, and mechanistic insights were gained by X-ray crystallography, cyclic voltammetry (CV), X-ray absorption spectroscopy (XAS), and DFT calculations. CV revealed an increased stability of cationic vs neutral Rh complexes toward oxidation. Comparison of solid-state and solution XAS (extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES)) data showed that the monomeric Rh complex [RhCl(2)] maintained its electronic state and coordination sphere in solution, whereas the dimeric Rh complex [RhCl(1)] 2 exchanges bridging chloro ligands by dioxane molecules in solution. In both 1,2-and 1,4-addition reactions, monomeric Rh complexes [RhCl(2)] and [RhOH 2 (2)]SbF 6 gave better yields as compared to dimeric complexes [RhCl(1)] 2 and [(Rh(1)) 2 Cl]SbF 6 . Regarding enantioselectivities, dimeric Rh species [RhCl(1)] 2 and [(Rh(1)) 2 Cl]SbF 6 performed better than monomeric Rh species in the 1,2-addition, while the opposite was true for the 1,4-addition. Neutral Rh complexes performed better than cationic complexes. Microemulsions improved the yields of 1,2-additions due to a most probable enrichment of Rh complexes in the amphiphilic film and provided a strong influence of the complex nuclearity and charge on the stereocontrol. A strong nonlinear-like effect (NLLE) was observed in 1,2-additions, when diastereomeric mixtures of ligands 1 and epi-1 were employed. The pronounced substrate dependency of the 1,4-addition could be rationalized by DFT calculations.

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Section: Discussionmentioning

confidence: 99%

Experimental and Theoretical Study on the Role of Monomeric vs Dimeric Rhodium Oxazolidinone Norbornadiene Complexes in Catalytic Asymmetric 1,2- and 1,4-Additions

et al. 2020

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“…In our group, we are interested in the effect of glycerol in metal‐catalyzed processes. In this context and with regard to homogeneous systems, we have recently found the non‐innocent role of glycerol in Rh‐catalyzed [2+2+1] Pauson–Khand (PK) carbocyclizations (Scheme ) 43. Actually, [{Rh(μ‐OMe)(cod)} 2 ] in the absence of any additional ligand led to the formation of the expected bicyclo[3.3.0]octenones, in contrast to the reactivity observed using conventional organic solvents, for instance THF or toluene, which require the presence of a phosphine ligand to direct the reaction towards the cyclization process.…”

Section: Metal Complexesmentioning

confidence: 99%

Glycerol as Suitable Solvent for the Synthesis of Metallic Species and Catalysis

Chahdoura¹,

Favier²,

Gómez³

2014

Chemistry A European J

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This Minireview considers the foremost reported works involving glycerol as a solvent in the synthesis of organometallic complexes and metallic nanoparticles. This analysis highlights their catalytic applications. A special emphasis is devoted to the ability of glycerol to immobilize nanometric species, which, in turn, enables an efficient recycling of the catalytic phase to give metal-free organic products.

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“…Several bonds are formed in "one-pot" in PKR with the simultaneous formation of three C-C bonds and the insertion of a carbonyl functionality from carbon monoxide. Chahdoura et al (2013b) developed PKR in neat glycerol (Fig. 30), while aware that its hydroxyl group reactivity could lead to by-products under strong basic conditions.…”

Section: Glycerol In Organometallic Reactionsmentioning

confidence: 99%

Catalysis in glycerol: a survey of recent advances

et al. 2015

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There is currently a significant increase in the use of glycerol as a renewable solvent for catalytic reactions. Glycerol has often been the solvent of choice in both homogeneous and heterogeneous catalyses, despite its high viscosity at ambient temperature and the low solubility of highly hydrophobic reagents found in glycerol. Its biodegradability and non-toxicity have led to reports of improved reaction performance and selectivity, as well as easier product separation and effective catalyst recycling. All relevant advances in this emerging field of "green" catalysis are thoroughly reviewed below.

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Glycerol – A Non‐Innocent Solvent for Rh‐Catalysed Pauson–Khand Carbocyclisations

Cited by 13 publications

References 39 publications

Experimental and Theoretical Study on the Role of Monomeric vs Dimeric Rhodium Oxazolidinone Norbornadiene Complexes in Catalytic Asymmetric 1,2- and 1,4-Additions

Experimental and Theoretical Study on the Role of Monomeric vs Dimeric Rhodium Oxazolidinone Norbornadiene Complexes in Catalytic Asymmetric 1,2- and 1,4-Additions

Glycerol as Suitable Solvent for the Synthesis of Metallic Species and Catalysis

Catalysis in glycerol: a survey of recent advances

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