(Perfluoro)alkylsilyl-Substituted 2-[Bis(4-aryl)phosphino]pyridines:  Synthesis and Comparison of Their Palladium Complexes in Methoxycarbonylation of Phenylacetylene in Regular Solvents and Supercritical CO<sub>2</sub>

Pater, Jeroen J. M. de; Maljaars, C. Elizabeth P.; Wolf, Elwin de; Lutz, Martin; Spek, Anthony L.; Deelman, Berth‐Jan; Elsevier, Cornelis J.; Koten, Gerard van

doi:10.1021/om050479+

Cited by 35 publications

(22 citation statements)

References 38 publications

(57 reference statements)

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“…A molybdenummediated intramolecular double allenic Pauson-Khand reaction was used to prepare dicyclopenta[a,e]pentalenes [1025]. (203) Palladium catalyzed a hydrocarbonylation of phenylethyne using carbon monoxide to form methyl 2-phenylpropenoate with high selectivity [1026]. Rhodium catalyzed a cyclocarbonylation of alkynes forming butenolides using methanal as the CO source (Eq.…”

Section: Carbonylations Of Alkynes (Including the Pauson-khand Reaction)mentioning

confidence: 99%

Transition metals in organic synthesis: Highlights for the year 2005

Söderberg

2008

Coordination Chemistry Reviews

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Section: Carbonylations Of Alkynes (Including the Pauson-khand Reaction)mentioning

confidence: 99%

Transition metals in organic synthesis: Highlights for the year 2005

Söderberg

2008

Coordination Chemistry Reviews

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“…High activity (TOF up to 8000 in methanol) and high selectivity (>99%) toward the branched ester product were reported [151]. Imidazolium-based ionic liquids with [PF 6 ] À , [BF 4 ] À , and [GaCl 4 ] À counterions were synthesized and used in hydroethoxycarbonylation of styrene.…”

Section: Hydroalkoxycarbonylationmentioning

confidence: 99%

Carbonylation of Alkenes and Dienes

Kégl

2008

Modern Carbonylation Methods

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In the beginning, only cobalt catalysts were utilized for hydroformylation under relatively vigorous conditions. The moderate selectivity of the generally more desired linear isomers, the substantial formation of by-products, and the low stability of the catalysts forced more appropriate catalytic systems to be developed. Using donor ligands such as phosphanes resulted in an increase in the linear selectivity. Rhodium-containing catalysts, however, permitted the use of much milder conditions in combination with suitable ligands. Other transition metals such as ruthenium, palladium, platinum, and iridium also tended to show activity for hydroformylation, albeit a vast majority of works on hydroformylation still concentrated on rhodium-containing systems. Cobalt CatalystsThe initial rate of Co 2 (CO) 8 -catalyzed cyclohexene hydroformylation, triethyl orthoformate carbonylation, and CoH(CO) 4 formation from Co 2 (CO) 8 and H 2 is reduced by the addition of dinitrogen, argon, or xenon. It is assumed that the additional gas competes with one or more reactants for a coordinatively unsaturated site responsible for their activation, thus affecting the reaction rate [1].The carbonylation reaction of propylene oxide in the presence of various [Lewis acid] þ [Co(CO) 4 ] À salts was investigated using in situ attenuated total reflection infrared (ATR-IR) spectroscopy. b-Alkoxy-acyl-cobalttetracarbonyl species were found to be key intermediates from which two reaction routes start depending on the applied Lewis acid. Labile Lewis acid-alkoxy combinations primarily favor the production of lactone products [2].The reaction of olefins (1-octene, 3,3-dimethylbutene, cyclohexene) introduced into a preequilibrated Co 2 (CO) 8 þ H 2 system was investigated by high-pressure infrared spectroscopy. Based on the observed induction period for the formation of the corresponding aldehyde, the decrease in HCo(CO) 4 concentration and increase in Co 2 (CO) 8 concentration during the induction period, the active catalytic species of the type H x Co y (CO) z was proposed [3]. Experiments with isotope mixtures of H 2 /D 2 in the gas phase during the various steps of the reaction showed that the ratio of H/D isotopes in the hydrocarbon portion of the aldehyde product correlates with the HCo(CO) 4 /DCo(CO) 4 ratio in solution, whereas the RC(¼O)H/RC(¼O)D product ratio correlates with the H 2 /D 2 in the gas phase. It was concluded that the dominant pathway for the hydrogenolysis step in this type of hydroformylation is the direct reaction of hydrogen or deuterium with the acyl complex intermediate [4].The effect of argon (280 bar) on the rate of aldehyde formation in 1-hexene hydroformylation catalyzed by Co 2 (CO) 8 at 50 C, 70 bar P(CO) and 85 bar P(H 2 ) in toluene was investigated by high-pressure FT-IR spectroscopy. The initial rate of the reaction was found to be reduced by the presence of argon. A similar effect was observed in the RhH(CO)(PPh 3 ) 3 -catalyzed cyclohexene hydroformylation reaction [5]. 162j 7 Carbonylation of Alkenes and D...

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“…Deelman, Elsevier and Van Koten et al recently reported on the methoxycarbonylation of phenylacetylene [38] by 1H,1H,2H,2H-perfluoroalkylsilyl-substitut- So far no studies that address the recycling of alkoxycarbonylation catalysts from supercritical CO 2 solutions have been reported. However, this may well become feasible in the near future by, e.g., nanofiltration [7e,39] or selective precipitation of the catalyst by variation of the pressure.…”

Section: Use Of Supercritical Co 2 In Alkoxycarbonylation Reactionsmentioning

confidence: 99%

“…Furthermore, one can find terms describing specific types of reactions, such as hydroxycarbonylation (formation of carboxylic esters), Figure 13. Functionalized 2-[bisA C H T U N G T R E N N U N G (4-aryl)phosphino]pyridine ligands used by Deelman, Elsevier, van Koten et al [38] …”

Section: Referencesmentioning

confidence: 99%

Multiphase Systems for the Recycling of Alkoxycarbonylation Catalysts

Pater¹,

Deelman²,

Elsevier³

et al. 2006

Adv Synth Catal

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This review evaluates the various multiphasic systems that have been developed for catalyst recycling in the context of alkoxycarbonylation of alkenes and alkynes. Immobilization of the catalyst on an insoluble support, such as silica, alumina, clay or a polymer, as well as immobilization in the inorganic phase of several liquid/liquid biphasic systems (aqueous/organic, ionic liquid/organic, fluorous/organic or supercritical CO 2 /organic) has been described. In several cases detailed information on the efficiency of catalyst separation and recycling is available. Most of the work was focused on the alkoxycarbonylation reactions of alkenes, for which several efficient methods for catalyst recycling were demonstrated. The recycling of catalyst through specific precipitation from supercritical CO 2 or selective dissolution in a fluorous phase, has received only scant attention but offers many opportunities for further improvement.

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(Perfluoro)alkylsilyl-Substituted 2-[Bis(4-aryl)phosphino]pyridines: Synthesis and Comparison of Their Palladium Complexes in Methoxycarbonylation of Phenylacetylene in Regular Solvents and Supercritical CO₂

Cited by 35 publications

References 38 publications

Transition metals in organic synthesis: Highlights for the year 2005

Transition metals in organic synthesis: Highlights for the year 2005

Carbonylation of Alkenes and Dienes

Multiphase Systems for the Recycling of Alkoxycarbonylation Catalysts

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(Perfluoro)alkylsilyl-Substituted 2-[Bis(4-aryl)phosphino]pyridines: Synthesis and Comparison of Their Palladium Complexes in Methoxycarbonylation of Phenylacetylene in Regular Solvents and Supercritical CO2

Cited by 35 publications

References 38 publications

Transition metals in organic synthesis: Highlights for the year 2005

Transition metals in organic synthesis: Highlights for the year 2005

Carbonylation of Alkenes and Dienes

Multiphase Systems for the Recycling of Alkoxycarbonylation Catalysts

Contact Info

Product

Resources

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(Perfluoro)alkylsilyl-Substituted 2-[Bis(4-aryl)phosphino]pyridines: Synthesis and Comparison of Their Palladium Complexes in Methoxycarbonylation of Phenylacetylene in Regular Solvents and Supercritical CO₂