Hydroformylation in the Realm of Scents

Gusevskaya, Elena V.; Jiménez-Pinto, Jhonny; Börner, Armin

doi:10.1002/cctc.201300474

Cited by 101 publications

(56 citation statements)

References 129 publications

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“…All these findings open a new window of opportunity to use abundant and cheap CO 2 as a source of CO for important industrial carbonylation processes, such as the production of fragrances. [59] Experimental Section…”

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confidence: 99%

Ruthenium‐Catalyzed Hydroformylation of Alkenes by using Carbon Dioxide as the Carbon Monoxide Source in the Presence of Ionic Liquids

et al. 2014

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Dedicated to the memory of Prof. Roberto F. Souza, one of the pioneers of ionic liquid phase organometallic catalysisThe reaction of [BMI·Cl] (BMI = 1-butyl-3-methylimidazolium) or [BMMI·Cl] (BMMI = 3-butyl-1,2-dimethylimidazolium) with Ru 3 (CO) 12 generates Ru-hydride-carbonyl-carbene species in situ that are efficient catalysts for a reverse water gas shift/ hydroformylation/hydrogenation cascade reaction. The addition of H 3 PO 4 increased the catalytic activity of the first step (i.e., the hydrogenation of CO 2 to CO). Under the optimized reaction conditions [120 8C and 6.0 MPa CO 2 /H 2 (1:1) for 17 h], cyclohexene and 2,2-disubstituted alkenes were easily functionalized to alcohols through sequential hydroformylation/carbonyl reduction.Carbon dioxide sequestration and its use as a feedstock in industrial processes are major challenges in the development of alternative greener and sustainable processes. [1] Indeed, several catalytic processes are under investigation, and they include the incorporation of CO 2 through the addition to epoxides to generate organic carbonates, diols, and polycarbonates by using either organic or metal-based catalysts. [2] However, the substitution of carbon monoxide (CO) by carbon dioxide (CO 2 ) in carbonylation reactions [3][4][5][6] may allow for new applications with broader use for this important and abundant but poorly reactive substrate. Indeed, at the industrial scale, the hydroformylation [7,8] of alkenes is one of the most important applications of homogeneous catalysis, and over 9 million tons of socalled oxo products, such as aldehydes and alcohols, are produced each year. [9] Rh-modified systems are the catalysts of choice for this reaction, as they are highly active and selective for the formation of aldehydes, [7,8] as well as for cascade reactions involving hydroformylation/Witting, [10] hydroaminomethylation sequences, [11,12] and hydroformylation/cyclization reactions. [13][14][15][16] Other metals, such as Pt and Ru, have been much less studied owing to their high hydrogenation activity, which results in the formation of large amounts of alkanes as byproducts. [17][18][19][20] However, the use of Rh-Ru bimetallic systems is of interest for the production of alcohols by hydroformylation/hydrogenation se-quences. [21][22][23][24][25] The differences in selectivity could be easily understood if we look at the hydroformylation and hydrogenation mechanisms catalyzed by Rh I and Ru 0 systems, as the active catalytic species under hydroformylation conditions are the RhÀH and the RuÀ(H) 2 species. [7][8][9]26] The accepted mechanism for the formation of MÀ(H) 2 is the homolytic cleavage of the HÀH bond, as the formation of MÀH occurs either by intramolecular (ligands) or intermolecular (external base) heterolysis of the HÀH bond, which favors the formation of MÀH species. [12,27,28] For instance, cationic [RuÀH] + species species are described as the catallytically active species in the Ru-catalyzed hydrogenation of acids, cyclic carbonates, and CO 2 to alcohol. [...

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Ruthenium‐Catalyzed Hydroformylation of Alkenes by using Carbon Dioxide as the Carbon Monoxide Source in the Presence of Ionic Liquids

et al. 2014

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“…As an application of the described catalytic system, the hydrogenation of 3-(1,3-benzodioxol-5-yil)-2-methyl-propenal (XIII), an α,β-unsaturated aldehyde precursor of Helional® (XIV), a valuable fragrance used in both feminine and masculine perfumes [13,[25][26][27][28][29][30][31][32][33][34], was studied (Scheme 3d, Table 5). A first experiment carried out at 30°C and 0.2 MPa of H 2 for 3 h and using a 1000/1 substrate to Pd molar ratio gave a very disappointing result (conversion 5%) (entry 1, Table 5).…”

Section: Catalytic Experimentsmentioning

confidence: 99%

An easily recoverable and recyclable homogeneous polyester-based Pd catalytic system for the hydrogenation of α,β-unsaturated carbonyl compounds

Bartoli

Rosi

Petrucci

et al. 2015

Catalysis Communications

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Homogeneous catalysis is an efficient tool to carry out hydrogenation processes but the major drawback is represented by the separation of the expensive catalyst from the product mixture. In this view we prepared a polyester-based Pd catalytic system that offers the advantages of both homogenous and heterogeneous catalyses: efficacy, selectivity and recyclability. Here its application in the hydrogenation of selected α,β-unsaturated carbonyl compounds is described.

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“…Rhodium catalyzed hydroformylation of simple and functionalized olefins has been well explored in the literature for the fine chemical synthesis . Hydroformylation of biomass derived olefins has great importance in fragrance and flavour industries . Biorenewable olefins such as eugenol, prenol, anethole and estragole represents a class of natural products which as significant potential for industrial manufacturing of perfumes, fragrances, flavors, food and pharmaceuticals .…”

Section: Introductionmentioning

confidence: 99%

Rhodium/Phosphine catalysed selective hydroformylation of biorenewable olefins

Jagtap

Bhanage

2018

Applied Organom Chemis

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This work reports rhodium catalyzed selective hydroformylation of natural olefins like eugenol, estragole, anethole, prenol and isoprenol using biphenyl based Buchwald phosphine ligands (S‐Phos (L1), t‐Bu XPhos (L2), Ru‐Phos (L3), Johnphos (L4) and DavePhos (L5). Ru‐Phos (L3) ligand exhibited high impact on the hydroformylation of eugenol providing high selectivity (90%) of linear aldehyde as major product. In addition, internal natural olefins like anethole and prenol provided moderate to high selectivity (65% and 85% respectively) of branched aldehydes as a major products. The various reaction parameters such as influence of ligands, P/Rh ratio, syngas pressure, temperature, time and solvents have been studied. A high activity and selectivity gained on the way to the linear aldehydes it may be due to the bulky, steric cyclohexyl and isopropoxy groups present in L3 phosphine ligand. Moreover, this catalytic system was smoothly converting natural olefins into corresponding linear and branched aldehydes with higher selectivity under the mild reaction conditions.

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Hydroformylation in the Realm of Scents

Cited by 101 publications

References 129 publications

Ruthenium‐Catalyzed Hydroformylation of Alkenes by using Carbon Dioxide as the Carbon Monoxide Source in the Presence of Ionic Liquids

Ruthenium‐Catalyzed Hydroformylation of Alkenes by using Carbon Dioxide as the Carbon Monoxide Source in the Presence of Ionic Liquids

An easily recoverable and recyclable homogeneous polyester-based Pd catalytic system for the hydrogenation of α,β-unsaturated carbonyl compounds

Rhodium/Phosphine catalysed selective hydroformylation of biorenewable olefins

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