Catalytic decarbonylation of aldehydes

Doughty, D.H.; Pignolet, L. H.

doi:10.1021/ja00490a061

Cited by 134 publications

(78 citation statements)

References 6 publications

(9 reference statements)

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“…In 1965 Tsuji and Ohno described the decarbonylation of aldehydes with stoichiometric amounts of Wilkinsons catalyst [RhA C H T U N G T R E N N U N G (PPh 3 ) 3 Cl]. [1] Three years later the same authors reported the first example of a rhodium-catalyzed decarbonylation with 0.5 % of Rh(CO)A C H T U N G T R E N N U N G (PPh 3 ) 2 Cl at temperatures above 200 8C.…”

Section: Introductionmentioning

confidence: 99%

“…[2] The high temperature did cause some side reactions and in 1978 Doughty and Pignolet described a milder procedure with RhA C H T U N G T R E N N U N G (dppp) 2 Cl [dppp = 1,3-bis(diphenylphosphino)propane]. [3] This catalyst was shown to perform the decarbonylation of heptanal and benzaldehyde at temperatures between 115 and 178 8C. [3] However, RhA C H T U N G T R E N N U N G (dppp) 2 Cl is not commercially available, which may explain why relatively little work has been published on the application of this method.…”

Section: Introductionmentioning

confidence: 99%

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A General and Convenient Method for the Rhodium‐Catalyzed Decarbonylation of Aldehydes

et al. 2006

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A practical protocol for the decarbonylation of a wide range of aldehydes has been developed by using commercially available RhCl 3 ·3 H 2 O and dppp in a diglyme solution. This method gives rise to decarbonylated products in good to high yield and is particularly useful because of its experimental simplicity, high generality and excellent level of functional group tolerance. The reaction has been applied in a tandem Oppenauer oxidation-decarbonylation sequence, which removes a hydroxymethyl group in one operation.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A General and Convenient Method for the Rhodium‐Catalyzed Decarbonylation of Aldehydes

et al. 2006

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“…Too strong coordination ability of dppe has prevented the interaction between Pd and substrates. Some reports describe that both the coordination ability and the flexibility of chelating ligand are important factors in related reactions 18,19) and this should be the case in this polycondensation. Low molecular weight when using dppe ligand was also observed in case of polyarylate synthesis by palladium-catalyzed carbonylationpolycondensation.…”

Section: Effect Of Palladium Complex Precursorsmentioning

confidence: 84%

New Heat-Resistant and Soluble Aramids Synthesized by Palladium-Catalyzed Carbonylation-Polycondensation

2002

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As a candidate for the alternate of conventional, insoluble thermosetting resins that are matrix components of fiber reinforced plastics (FRP), soluble and heat-resistant aramids (wholly aromatic polyamides) were synthesized. To obtain rigid biphenyl-containing aramid, one-step procedure from dihalobiphenyl and aromatic diamine by palladium-catalyzed carbonylation-polycondensation was successfully applied. Reaction parameters, such as base, solvent, palladium-phosphine catalyst and CO pressure in the reaction of 2,7-dibromo-9,10-dihydrophenanthrene (1) and 4,4 -diaminodipheyl ether (2a), were very important for successful synthesis. They affected the molecular weight of resulting aramid significantly. Under optimum conditions, poly[amino-1,4-phenyleneoxy-1,4-phenyleneaminocarbonyl(9,10-dihydro-2,7-phenanthrenediyl)carbonyl] (3a) was obtained in 99% yield with high molecular weight (polystyrene equivalent M w = 128100). The procedure was applied to some other diamines. The aramid 3a was heat-resistant and soluble in polar organic solvent. On the basis of thermal analysis, 10% weight loss temperature (T 10 ) of the aramid was 461 • C. The tensile strength and tensile modulus were 48 MPa and 1.6 GPa, respectively; these properties are roughly in the same level as those of conventional unsaturated polyester resin. Judging from the data, aramid 3a is applicable for matrix of FRP. Some other aramids exhibited similar properties.

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“…This led us to explore the possibility of a tandem catalytic scheme using the rhodium complex 2, which is effective for aldehyde decarbonylation [19]. Thus, if an α-HA were formed by primary alcohol dehydrogenation by 1, this may be intercepted in situ by decarbonylation (Scheme 3).…”

Section: Tandem Catalysis Studies With 12-diolsmentioning

confidence: 99%

Catalytic dehydrogenation of 1,2- and 1,3-diols

Weber

Ford

2016

Journal of Molecular Catalysis A: Chemical

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Abstract:Described are studies of the dehydrogenation of 1,2-and 1,3-diols in homogenous solutions catalyzed by {[2,5-diphenyl-3,4-ditoluyl-(η 5 -C4CO)]2H}Ru2(CO)4(μ-H) (otherwise known as the Casey/Shvo catalyst). Both in the presence and absence of a dihydrogen acceptor, these reactions led to the analogous α-hydroxyketone as the only organic product. Isotopic labeling studies indicate that this product arises from reversible dehydrogenation/hydrogenation reactions, resulting in formation of the thermodynamically favored α-hydroxyketone. When this catalytic dehydrogenation was carried out in the presence of the rhodium decarbonylation catalyst Rh(dppp)2Cl (dppp = 1,3-bis(diphenylphosphino)propane), modest amounts of carbon monoxide result, suggesting that the dehydrogenation does generate at least some aldehydes that are intercepted by this catalyst. However, the efficiency of the latter reaction is poor.

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Catalytic decarbonylation of aldehydes

Cited by 134 publications

References 6 publications

A General and Convenient Method for the Rhodium‐Catalyzed Decarbonylation of Aldehydes

A General and Convenient Method for the Rhodium‐Catalyzed Decarbonylation of Aldehydes

New Heat-Resistant and Soluble Aramids Synthesized by Palladium-Catalyzed Carbonylation-Polycondensation

Catalytic dehydrogenation of 1,2- and 1,3-diols

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