A Large-Scale Synthesis of α-Olefins and α,ω-Dienes

Kraus, George A.; Riley, Sean

doi:10.1055/s-0031-1290400

Cited by 46 publications

(33 citation statements)

References 6 publications

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“…Nevertheless, catalyst turnovers up to 400 could be achieved for these challenging substrates. Compared to previous reports by Miller12a and Kraus,12b our reaction exhibits a much broader scope, does not require distillation of the olefin products to maintain high selectivity, and is compatible with various heteroatom‐containing functional groups.…”

Section: Methodsmentioning

confidence: 81%

“…Various transition metals including rhodium,10 iridium,11 palladium,12 and iron13 have been shown to catalyze decarbonylative dehydration reactions. To date, palladium has demonstrated the highest activity, and catalyst loadings as low as 0.01 mol% have been reported independently by Miller12a and Kraus12b (Scheme A). Unfortunately, their methods require very high temperatures (230–250 °C).…”

Section: Methodsmentioning

confidence: 97%

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Keine Angst vor Peroxiden

Brandl

Täuscher

Weiss

2015

Chemie in nserer Zeit

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Mit Peroxiden assoziieren viele Menschen gefährliche, hochexplosive Chemikalien, die mitunter für terroristische Anschläge verwendet werden. Der vorliegende Beitrag versucht, die latente Angst vor einem Gebrauch peroxidhaltiger Produkte zu nehmen. Es wird ein Überblick über Vorkommen in der Natur, industrielle Herstellung, chemische Strukturen und Anwendungsmöglichkeiten der verschiedenen Peroxid‐Gruppen gegeben. Ein Schwerpunkt ist die Hydroperoxidbildung von Fetten, Ölen, Ethern und bestimmten Kohlenwasserstoffen bei deren Autoxidation an Luft. Effektvolle Chemolumineszenzexperimente von hydroperoxidhaltigen Verbindungen bei deren katalytischen Thermolysen mit fluoreszenzfähigen, organischen Magnesium‐ und oder Zink‐Komplexsalzen werden beschrieben.

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Section: Methodsmentioning

confidence: 81%

Section: Methodsmentioning

confidence: 97%

Keine Angst vor Peroxiden

Brandl

Täuscher

Weiss

2015

Chemie in nserer Zeit

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“…[3][4][5] Among them, homogeneous palladium-based catalysts have demonstrated the highest catalytic activity, yielding fatty acid conversions around 60-75 mol% and selectivity values higher than 97 mol%, with a catalyst loading as low as 0.01 mol% in solution. 6,7 Nevertheless, these systems operate at high reaction temperatures (230-250°C) and the olefin product must be continuously distilled to avoid double bond isomerization, thereby maintaining the high selectivity. In this respect, some works have succeeded in reducing the reaction temperature to 110°C, reaching moderate α-olefin productivity (turnover number (TON) <33, turnover frequency (TOF) ∼2 h −1 , α-selectivity >97 mol%), albeit at the expense of increasing the catalyst loading in solution (3 mol%).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of a supported Pd complex on carbon nanofibers for the selective decarbonylation of stearic acid to 1-heptadecene: the importance of subnanometric Pd dispersion

Ochoa

Henao

Fuertes

et al. 2020

Catal. Sci. Technol.

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Production of linear α-olefins from renewable sources is gaining increasing attention because it allows the transition from the current petrochemical synthesis route to a more sustainable scenario. In this work, we describe the synthesis and characterization of an innovative catalyst based on a di-μ-chloro-bisĳpalladiumĲII) anthranilate] complex highly dispersed by incipient wetness impregnation over acyl chlorinated carbon nanofibers. The subnanometric dispersion of the metal complex allowed higher catalytic efficiency for the selective decarbonylation of stearic acid to 1-heptadecene as compared to the reference homogenous catalyst. The best catalytic performance (90 mol% selectivity, 71 mol% conversion, and TON = 484) was achieved under mild reaction conditions (atmospheric pressure, 140°C) with a Pd loading in solution of 0.14 mol%. The post-mortem catalyst characterization and the recyclability tests evidenced the high stability of the catalyst. The highly dispersed catalyst developed in this work provides new opportunities in the rational design of more efficient catalytic systems for the sustainable transformation of fatty acids.

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“…LAOs may be obtained from fatty acids using homogenous- [12][13][14][15][16][17], heterogeneous- [18], and bio-catalysts [19][20][21]. The highest activities and selectivities have so far been obtained with homogenous catalysts [2,14,22]. Homogeneously catalyzed decarbonylative dehydration has proven to be a promising reaction in the production of LAOs [12][13][14][15][22][23][24][25][26][27][28][29][30], as well as in the toolbox of the synthetic organic chemist [31].…”

Section: Introductionmentioning

confidence: 99%

“…With this promising outlook, transition-metal catalysts based on palladium [12][13][14][15]22,25,29,30,32], rhodium [14,23], iridium [27,33], nickel, [24,34], and iron [28] have been developed. Palladium-based catalysts have so far reached the highest activities [14].…”

Section: Introductionmentioning

confidence: 99%

The Mechanism of Rh-Catalyzed Transformation of Fatty Acids to Linear Alpha olefins

et al. 2017

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Linear alpha olefins (LAOs) are key commodity chemicals and petrochemical intermediates that are currently produced from fossil resources. Fatty acids are the obvious renewable starting material for LAOs, which can be obtained via transition-metal-catalyzed decarbonylative dehydration. However, even the best catalysts that have been obtained to date, which are based on palladium, are not active and stable enough for industrial use. To provide insight for design of better catalysts, we here present the first computationally derived mechanism for another attractive transition-metal for this reaction, rhodium. By comparing the calculated mechanisms and free energy profiles for the two metals, Pd and Rh, we single out important factors for a facile, low-barrier reaction and for a stable catalyst. While the olefin formation is rate limiting for both of the metals, the rate-determining intermediate for Rh is, in contrast to Pd, the starting complex, (PPh 3) 2 Rh(CO)Cl. This complex largely draws its stability from the strength of the Rh(I)-CO bond. CO is a much less suitable ligand for the high-oxidation state Rh(III). However, for steric reasons, rhodium dissociates a bulkier triphenylphosphine and keeps the carbonyl during the oxidative addition, which is less favorable than for Pd. When compared to Pd, which dissociates two phosphine ligands at the start of the reaction, the catalytic activity of Rh also appears to be hampered by its preference for high coordination numbers. The remaining ancillary ligands leave less space for the metal to mediate the reaction.

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A Large-Scale Synthesis of α-Olefins and α,ω-Dienes

Abstract: The decarbonylation of carboxylic acids or dicarboxylic acids in the presence of a palladium catalyst above 190°C in the absence of a solvent constitutes a mild method for the large-scale synthesis of α-olefins and α,ω-dienes.

Cited by 46 publications

References 6 publications

Keine Angst vor Peroxiden

Keine Angst vor Peroxiden

Synthesis and characterization of a supported Pd complex on carbon nanofibers for the selective decarbonylation of stearic acid to 1-heptadecene: the importance of subnanometric Pd dispersion

The Mechanism of Rh-Catalyzed Transformation of Fatty Acids to Linear Alpha olefins

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