Direct formation of alcohols by hydrocarbonylation of alkenes under mild conditions using rhodium trialkylphosphine catalysts

MacDougall, Joanna K.; Simpson, Michael; Green, Michael J.; Cole‐Hamilton, David J.

doi:10.1039/dt9960001161

Cited by 89 publications

(69 citation statements)

References 10 publications

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“…Variation of the temperature in the range 80-120 8C (entries 3, 5, 6) and of the CO/H 2 pressures from 10:30 to 30:10 atm (entries 3, 7, 8) did not appreciably affect the regioselectivity. More expectedly, the [dppe]/ [Rh] ratio had a pronounced influence on both the activity and regioselectivity: the activity was optimal at a moderate [dppe]/ [Rh] ratio of 5 (entries 3, [9][10][11][12]. These results are consistent with stabilization of the active Rh species in the presence of a slight excess of diphosphine, whereas more ligand competes with substrate coordination.…”

Section: Entrysupporting

confidence: 57%

“…All the catalyst systems were found to give high and selective conversions of VMD into a mixture of the branched (1) and linear (2) aldehydes (Scheme 1). Neither the hydrogenation product of VMD (3) nor the homologous alcohols 4 and 5, potentially generated directly from VMD [10] or derived from subsequent reduction of the aldehyde functionality respectively in 1 and 2, were detected (< 0.1 %) under the conditions used (by-products 3-5 were independently synthesized and characterized; see the Experimental Section and Supporting Information). The highest activities were obtained by using simple monophosphite ligands (entries 7-9), yet the regioselectivity was always very poor, giving close to 1:1 mixtures of the linear and branched aldehydes, in contrast to patent claims (based on experiments performed under slightly different reaction conditions).…”

Section: Hydroformylation Of Vmd Under Homogeneous Conditionsmentioning

confidence: 99%

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Rhodium‐Catalyzed Homogeneous and Aqueous Biphasic Hydroformylation of the Acrolein Acetal 2‐Vinyl‐5‐Methyl‐1,3‐Dioxane

Ternel¹,

Dubois²,

Couturier³

et al. 2013

ChemCatChem

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International audienceThe rhodium-catalyzed hydroformylation of 2-vinyl-5-methyl-1,3-dioxane (VMD), the acetal derived from acrolein and 2-methyl-1,3-propanediol, has been investigated. Under homogeneous conditions, phosphane-based catalysts afforded perfect chemoselectivity for the aldehydes. Catalysts based on diphosphine ligands with a narrow bite angle of approximately 85°, such as 1,2-bis(phenylphosphino)ethane, were found to favor the branched aldehyde 2, with selectivities of up to 78 %, whereas diphosphine ligands with a large bite angle of approximately 110°, such as xantphos, produce the linear aldehyde 1 with up to 91 % selectivity. Control of the 1/2 regioselectivity by means of the P[BOND]Rh[BOND]P bite angle was ascertained with a variety of ethylene-, hydrazino- and CNC-bridged diphosphines, irrespective of electronic factors induced by these ligands. Under aqueous biphasic conditions, chemoselective hydroformylation of VMD proved feasible only with disulfonated xantphos; in this case, remarkable activities (turnover frequencies of up to 1075 molaldehyde molRh−1 h−1 at 120 °C) were observed, with up to 82 % yield for the linear aldehyde. On the other hand, the catalyst based on tetrasulfonated dppe systematically induced the formation of very large amounts of the hydrogenated product

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Section: Entrysupporting

confidence: 57%

Section: Hydroformylation Of Vmd Under Homogeneous Conditionsmentioning

confidence: 99%

Rhodium‐Catalyzed Homogeneous and Aqueous Biphasic Hydroformylation of the Acrolein Acetal 2‐Vinyl‐5‐Methyl‐1,3‐Dioxane

Ternel¹,

Dubois²,

Couturier³

et al. 2013

ChemCatChem

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“…This has indeed been observed in several cases, using strongly electron-donating phosphines [67][68][69] or amines [70,71] as ligands. The most detailed studies on this topic have been carried out by Cole-Hamilton and coworkers, who used [Rh 2 (OAc) 4 ]/PEt 3 as a catalyst [72][73][74]. In the hydroformylation of hex-1-ene in aprotic solvents, hydrogenation of the initially formed heptanal and 2-methylhexanal products to the corresponding alcohols occurs as the reactions proceeds.…”

Section: Rhodium Catalystsmentioning

confidence: 99%

Homogeneous Hydrogenation of Aldehydes, Ketones, Imines and Carboxylic Acid Derivatives: Chemoselectivity and Catalytic Activity

Clarke¹,

Roff²

2006

The Handbook of Homogeneous Hydrogenation

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414Scheme 15.1 Hydrogenation of n-butyraldehyde. Table 15.1 Hydrogenation of aldehydes with [IrH 3 (PPh 3 ) 3 ] in acetic acid. Substrate Catalyst [mol.%] Temperature [8C] Yield [%] TON TOF [h -1 ] 0.022 80 73 3280 492 0.023 110 82 3540 177 0.032 90 64 2000 89 0.039 110 80 2030 81 0.013 110 98 7780 259 examined for a,b-unsaturated aldehydes (Scheme 15.2). Using the [IrH 3 (PPh 3 ) 3 ] complex in acetic acid for the hydrogenation of crotonaldehyde resulted in the formation of the saturated alcohol (Scheme 15.3). It was also noted that this catalyst did not allow for ketone hydrogenation at 10 bar. Other attempts to use iridium PPh 3 complexes such as [IrCl(PPh 3 ) 3 ], [IrCl(CO)(PPh 3 ) 2 ], [Ir(ClO 4 )(CO)(PPh 3 ) 2 ] and [Ir(CO)(PPh 3 ) 3 ]ClO 4 to hydrogenate unsaturated aldehydes did not yield great results [3], mainly because these catalysts suffered from low activity and selectivity.The catalytic system of [Ir(COD)Cl] 2 with an excess of the bulky phosphine P(o-MeOPh) 3 under transfer hydrogenation conditions of propan-2-ol and KOH was used successfully in the selective hydrogenation of cinnamaldehyde (Scheme 15.4) [4]. Selectivity and activity were found to increase with increasing P/Ir ratios, and complete conversion was achieved in as little as 5 minutes (turnover frequency (TOF) *6000 h -1 ). Hydrogenation of Aldehydes 415Scheme 15.2 Distribution of products in the hydrogenation of a,b-unsaturated aldehydes. Scheme 15.3 Hydrogenation of crotonaldehyde with [IrH 3 (PPh 3 ) 3 ] in acetic acid. Scheme 15.4 Transfer hydrogenation of cinnamaldehyde.Using molecular hydrogen as the reducing agent, [Ir(COD)(OCH 3 )] 2 with an excess of tertiary phosphine was better than [Ir(COD)Cl] 2 for the selective hydrogenation of cinnamaldehyde [5]. In these studies, a great dependence on solvent and ligand was reported. A variety of different phosphines, which were markedly different in their steric and electronic properties, were examined in this reaction. In propan-2-ol the most effective phosphine was PCy 2 Ph which gave 94% yield (TOF 235 h -1 ) of the unsaturated alcohol in a 2 h reaction under 30 bar H 2 at 100 8C. Phosphines such as PCyPh 2 , PPhPr i 2 , PPh 2 Pr i and PEtPh 2 were also effective in giving over 95% selectivity. The less-effective phosphines were PEt 2 Ph, PMePh 2 , PBu i 3 and PMe 2 Ph. Reactions that were performed in toluene were generally less effective.More recent advances in iridium-catalyzed aldehyde hydrogenation have been through the use of bidentate ligands [6]. In the hydrogenation of citral and cinnamaldehyde, replacing two triphenylphosphines in [IrH(CO)(PPh 3 ) 3 ] with bidentate phosphines BDNA, BDPX, BPPB, BISBI and PCP ( Fig. 15.1) led to an increase in catalytic activity. a) Selectivity of allylic alcohol formed as a percentage of total hydrogenation products. b) TOF (h -1 ) expressed for conversion of starting material. Hydrogenation of Aldehydes 419Scheme 15.5 Preparation of cationic DiPFc catalyst.

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“…Cole-Hamilton and coworkers [82] found activity for alkylphosphine complexes when RhH(PEt 3 ) 3 was used as the precursor, but at higher temperatures as expected. Under the reaction conditions RhH(CO)(PEt 3 ) 3 is the major species present.…”

Section: Monophosphinesmentioning

confidence: 99%

Carbon Monoxide as a Chemical Feedstock: Carbonylation Catalysis

Leeuwen

Freixa

2006

Activation of Small Molecules

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Direct formation of alcohols by hydrocarbonylation of alkenes under mild conditions using rhodium trialkylphosphine catalysts

Abstract: Solvent contains ethanol. In ['HJthf. ' v(Rh-H) 1884 cm I . ' In C6D6. ' v(Rh-H) 1880 cm I . In C2D,0D. ' In CD2C12. j Solvent contains CF,CH20H.

Cited by 89 publications

References 10 publications

Rhodium‐Catalyzed Homogeneous and Aqueous Biphasic Hydroformylation of the Acrolein Acetal 2‐Vinyl‐5‐Methyl‐1,3‐Dioxane

Rhodium‐Catalyzed Homogeneous and Aqueous Biphasic Hydroformylation of the Acrolein Acetal 2‐Vinyl‐5‐Methyl‐1,3‐Dioxane

Homogeneous Hydrogenation of Aldehydes, Ketones, Imines and Carboxylic Acid Derivatives: Chemoselectivity and Catalytic Activity

Carbon Monoxide as a Chemical Feedstock: Carbonylation Catalysis

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