Selective hydrogenation of .alpha.,.beta.-unsaturated aldehydes in aqueous organic two-phase solvent systems using ruthenium or rhodium complexes of sulfonated phosphines

Grosselin, Jean Michel.; Mercier, C.; Allmang, G.; Grass, F.

doi:10.1021/om00053a014

Cited by 213 publications

(56 citation statements)

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“…[Pd] = PdBr 2 or (Ph 3 P) 2 This concept is applicable to a wide variety of transition metal-catalyzed processes [42], for example, the chemoselective hydrogenation of unsaturated aldehydes (Fig. 9) [43].…”

Section: Catalysis In Novel Mediamentioning

confidence: 99%

Atom efficiency and catalysis in organic synthesis

Sheldon

2000

Pure and Applied Chemistry

731

322

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Abstract:The key to waste minimization in fine chemicals manufacture is the widespread substitution of classical organic syntheses employing stoichiometric amounts of inorganic reagents with cleaner, catalytic alternatives. The E factors (by waste per kg product) of chemical processes increase dramatically on going downstream from bulk to fine chemicals and pharmaceuticals, mainly owing to the use of "stoichiometric" methods. The concept of atom efficiency is a useful tool for rapid evaluation of the amount of waste generated by alternative processes. The general theme of atom-efficient, catalytic processes is illustrated with industrially relevant examples. These include catalysis by solid acids and bases, catalytic reductions and oxidations, catalytic C-C bond formation, asymmetric catalysis, biocatalysis, and catalysis in novel media (aqueous and fluorous biphasic systems, supercritical fluids, and ionic liquids).

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Section: Catalysis In Novel Mediamentioning

confidence: 99%

Atom efficiency and catalysis in organic synthesis

Sheldon

2000

Pure and Applied Chemistry

731

322

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“…Such a selective hydrogenation is one of important reactions for the production of perfume and fine chemicals [5][6][7]. The selectivity for the corresponding unsaturated alcohol, cinnamyl alcohol (COL), can be improved by multiphase reactions using water -organic liquid systems [8][9][10][11][12][13][14][15][16][17][18], water -dense CO 2 systems [19], and supported liquid phase catalysts [20,21]. The present authors have recently indicated that COL is selectively produced with a water-soluble complex of ruthenium -TPPTS (trisodium tris(m-sulfonatophenyl)phosphine), which exists in an aqueous phase being in contact with a bulk CAL phase in toluene, pure CAL, or dense CO 2 ( Fig.…”

Section: Introductionmentioning

confidence: 99%

Recyclability of water-soluble ruthenium–phosphine complex catalysts in multiphase selective hydrogenation of cinnamaldehyde using toluene and pressurized carbon dioxide

Fujita

Akihara

Arai

2006

Journal of Molecular Catalysis A: Chemical

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The recyclability of water-soluble ruthenium -phosphine complex catalysts was investigated in water -toluene and in water -pressurized carbon dioxide systems for selective hydrogenation of trans-cinnamaldehyde (CAL). For the first hydrogenation run, the selectivity for cinnamyl alcohol (COL) is high for both toluene and dense CO 2 , because of interfacial catalysis in which the reaction mainly occurs at the interface between the aqueous phase and the other toluene or dense CO 2 phase. The total CAL conversion and the COL selectivity decrease on the second run, more significantly with dense CO 2 than toluene. On the subsequent runs, however, less significant changes were observed. During the first run, the active metal complexes should change to much less active ones such as Ru(H) 2 L n (TPPTS) m (L=COL) by accumulation of the main product of COL. This structural change may occur more easily in multiphase hydrogenation with dense CO 2 than that with toluene, probably because the solubility in the dense CO 2 gas phase is even smaller than that in toluene. For homogeneous reaction of COL in aqueous phase, Ru(H) 2 L n (TPPTS) m catalyzes the isomerization to HCAL compared with the hydrogenation to hydrocinnamyl alcohol. With those complexes, however, the selectivity for COL is still comparable to that for HCAL for multiphase hydrogenation reactions because the hydrogenation of an ampholytic substrate of CAL occurs mainly at interface between water and toluene or dense CO 2 gas phase. Interactions of CO 2 molecules with CAL would also increase the reactivity of carbonyl group of the substrate.

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Section: Scheme 1 Aqueous Biphasic Hydrogenation Of 2-cyclohexen-1-omentioning

confidence: 99%

“…[19][20][21][22][23]. The well-known Rh(I)/TPPTS complex, employed in the famous Ruhrchemie/Rhône-Poulenc biphasic process for the hydroformylation of propene [4][5][6][7], hydrogenates ␣,␤-unsaturated aldehydes into the corresponding saturated aldehydes, without decarbonylation, as in the case of cinnamaldehyde that can be selectively reduced to 3-phenylpropanal [19,24,25]. Recently we reported some results obtained in cinnamaldehyde hydrogenation by using the catalytic system Rh(CO) 2 acac/TPPTS in the biphasic system water/toluene, at 60 • C and 5 MPa of H 2 for 22 h: practically quantitative conversions were obtained but, even if 3-phenylpropanal (VI) was the main product, alcohols VII and VIII were formed, too [11].…”

Section: Scheme 1 Aqueous Biphasic Hydrogenation Of 2-cyclohexen-1-omentioning

confidence: 99%

Simple and efficient water soluble thioligands for rhodium and iridium catalyzed biphasic hydrogenation

Dio

Marchetti

Paganelli

et al. 2011

Applied Catalysis A: General

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a b s t r a c tThe activity of catalytic systems derived from the interaction between Rh(CO) 2 acac and [Ir(COD)Cl] 2 , respectively, with the water soluble thioligands (L)-Cysteine (1) and (S)-Captopril (2), was tested in the aqueous biphasic hydrogenation of some representative ␣,␤-unsaturated compounds as 2-cyclohexen-1-one (I), trans-cinnamaldehyde (V) and [3-(1,3-benzodioxol-5-yl)-2-methylpropenal] (X), precursor of the fragrance Helional ® (XI). The precatalyst Rh/Cap was able to hydrogenate cyclohexenone even at low pressure at 60• C in a neutral medium while Rh/Cy required either higher pressure and temperature or an alkaline medium. The iridium based catalysts, Ir/Cy and Ir/Cap, showed an analogous trend though their activities were lower than those of the related rhodium catalysts. All the catalysts were easily recycled without significant loss of activity. The rhodium catalysts were also used in the hydrogenation of the above aldehydes V and X and their activity was strongly enhanced when ethylene glycol was used as organic solvent or co-solvent.

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Selective hydrogenation of .alpha.,.beta.-unsaturated aldehydes in aqueous organic two-phase solvent systems using ruthenium or rhodium complexes of sulfonated phosphines

Cited by 213 publications

References 0 publications

Atom efficiency and catalysis in organic synthesis

Atom efficiency and catalysis in organic synthesis

Recyclability of water-soluble ruthenium–phosphine complex catalysts in multiphase selective hydrogenation of cinnamaldehyde using toluene and pressurized carbon dioxide

Simple and efficient water soluble thioligands for rhodium and iridium catalyzed biphasic hydrogenation

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