Rhodium catalyzed aqueous biphasic hydroformylation of naturally occurring allylbenzenes in the presence of water-soluble phosphorus ligands

Baricelli, Pablo J.; Rodríguez, Mariandry; Melean, Luis G.; Alonso, María Modroño; Borusiak, Margarita; Rosales, Merlín; González, Beatríz; Oliveira, Kelley C.B.; Gusevskaya, Elena V.; Santos, Eduardo N. dos

doi:10.1016/j.apcata.2014.11.028

Cited by 22 publications

(5 citation statements)

References 29 publications

(28 reference statements)

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“…[27] We have also established ar oute to produce octyl methoxycinnamate, am ajor UV-A filter used in sunscreen lotions, through the Rucatalyzed cross-metathesis of the naturallyo ccurring anethole with the commodity chemical 2-ethylhexyl acrylate. [27] We have also established ar oute to produce octyl methoxycinnamate, am ajor UV-A filter used in sunscreen lotions, through the Rucatalyzed cross-metathesis of the naturallyo ccurring anethole with the commodity chemical 2-ethylhexyl acrylate.…”

Section: Introductionmentioning

confidence: 99%

“…In ar ecent example, we have developed ao ne-step synthesis of the commercialf ragrance Canthoxal through the hydroformylation of the naturally occurring estragole, employing water as as olvent in ar ecyclable biphasic system. [27] We have also established ar oute to produce octyl methoxycinnamate, am ajor UV-A filter used in sunscreen lotions, through the Rucatalyzed cross-metathesis of the naturallyo ccurring anethole with the commodity chemical 2-ethylhexyl acrylate. [28] More generally, the cross-metathesis of natural products with acrylates is an excellent approachf or the synthesis of monomers, polymers, [29,30] or fine chemicals.…”

Section: Introductionmentioning

confidence: 99%

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p‐Cymene as Solvent for Olefin Metathesis: Matching Efficiency and Sustainability

Granato

Santos

2017

ChemSusChem

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The underexploited biorenewable p-cymene is employed as a solvent for the metathesis of various substrates. p-Cymene is a nontoxic compound that can be obtained in large amounts as a side product of the cellulose and citrus industry. For the cross-metathesis of estragole with methyl acrylate, this solvent prevents the consecutive double-bond isomerization of the product and affords the best yield of all solvents tested. Undesired consecutive isomerization is a major challenge for many substrates in olefin metathesis, including pharmaceutical precursors, and the use of p-cymene as a solvent may be a way to prevent it. This solvent results in a better metathesis performance than toluene for the three substrates tested in this work, matching its performance for two other substrates.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

p‐Cymene as Solvent for Olefin Metathesis: Matching Efficiency and Sustainability

Granato

Santos

2017

ChemSusChem

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“…Regarding to catalyst recovery and reuse, some of us published recently a methodology for the hydroformylation of 2-propenylbenzenes in which the catalyst is supported in an aqueous phase by means of the water-soluble sulfonated version of DPPE, inter alia. [36] The catalyst is recovered by decantation of the aqueous phase after hydroformylation. We believe that this system could be adapted for the 1-arylbutadienes 3a-c, and this should be a matter for further studies.…”

Section: J O U R N a L P R E -P R O O Fmentioning

confidence: 99%

Tandem hydroformylation/isomerization/hydrogenation of bio-derived 1-arylbutadienes for the regioselective synthesis of branched aldehydes

Vieira

Granato

Gusevskaya

et al. 2020

Applied Catalysis A: General

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The rhodium-catalyzed hydroformylation of 1-arylbutadienes derived from lignocellulosic bio-resources has been carried out in toluene and green solvents. In the presence of DPPE and XANTPHOS ligands, a regioselective Markovnikov Rh-H insertion takes place resulting in branched aldehydes in high selectivity, which contrasts with previous results obtained from aliphatic conjugated dienes. Depending on the nature of the diphosphine ligand, conjugated enals or saturated aldehydes are obtained in good to excellent selectivity. The later have a potential interest for fragrance industry, as they are homologous to commercial fragrance ingredients.

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“…First-generation catalysts generally require a higher temperature and pressure to avoid degradation of the catalytically active species in the hydroformylation reaction. This facilitated improvements being made with respect to ligands and transition metals used for selectivity, stability, and reduction of byproduct formation. − Second-generation catalysts based on modified phosphine ligands and rhodium as a metal center were first discovered by Wilkinson et al in the 1960s, with [RhCl(PPh 3 ) 3 ] being a classic example. In addition to greater stability at lower temperature and pressure, modifications made to the ligands of rhodium-based catalyst precursors demonstrated advantages such as increased selectivity toward linear aldehydes and minimal isomerization of the substrate .…”

Section: Introductionmentioning

confidence: 99%

Bimetallic Paddlewheel-type Dirhodium(II,II) Acetate and Formamidinate Complexes: Synthesis, Structure, Electrochemistry, and Hydroformylation Activity

et al. 2020

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Classical hydroformylation catalysts use mononuclear rhodium(I) complexes as precursors; however, very few examples of bimetallic systems have been reported. Herein, we report fully substituted dirhodium(II,II) complexes (C1−C6) containing acetate and diphenylformamidinate bridging ligands (L1−L4). The structure and geometry around these paddlewheeltype, bimetallic cores were confirmed by single-crystal X-ray diffraction. The complexes C3−C6 show electrochemical redox reactions, with the expected reduction (Rh 2 4+/3+ ) and two oxidation (Rh 2 4+/5+ and Rh 2 5+/6+ ) electron transfer processes. Furthermore, the bimetallic complexes were evaluated as catalyst precursors for the hydroformylation of 1-octene, with the acetate-containing complexes (C1 and C2) showing near quantitative conversion (>99%) of 1-octene, excellent activity and chemoselectivity toward aldehydes (>98%), with moderate regioselectivity toward linear products. Replacement of the acetate with diphenylformamidinate ligands (complexes C3−C6) yielded moderate-togood chemoselectivity and regioselectivity, favoring linear aldehydes.

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Rhodium catalyzed aqueous biphasic hydroformylation of naturally occurring allylbenzenes in the presence of water-soluble phosphorus ligands

Cited by 22 publications

References 29 publications

p‐Cymene as Solvent for Olefin Metathesis: Matching Efficiency and Sustainability

p‐Cymene as Solvent for Olefin Metathesis: Matching Efficiency and Sustainability

Tandem hydroformylation/isomerization/hydrogenation of bio-derived 1-arylbutadienes for the regioselective synthesis of branched aldehydes

Bimetallic Paddlewheel-type Dirhodium(II,II) Acetate and Formamidinate Complexes: Synthesis, Structure, Electrochemistry, and Hydroformylation Activity

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