Dual-catalytic decarbonylation of fatty acid methyl esters to form olefins

Fieser, Megan E.; Schimler, Sydonie D.; Mitchell, Lauren A.; Wilborn, Emily G.; John, Alex; Hogan, Levi T.; Benson, Brad; LaPointe, Anne M.; Tolman, William B.

doi:10.1039/c8cc03823f

Cited by 14 publications

(9 citation statements)

References 43 publications

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“…Carboxylic acid decarbonylation reactions have been studied to understand the reaction mechanism and improve transition-metal catalysis . Rather than directly decarbonylating the biomass-sourced carboxylic acid, it is often necessary to activate the weakly reactive carboxylic acid substrate to afford an anhydride − or ester − derivative. These electron-withdrawing groups facilitate a reaction with a transition-metal catalyst that may then enter the catalytic cycle.…”

Section: Feedstocksmentioning

confidence: 99%

“…In an effort to circumvent isolation of the activated ester intermediate, Fieser et al established a dual-catalytic method to convert fatty acid methyl esters to a mixture of olefins (Scheme ). Methyl palmitate ( 2 - 35 ) first underwent ZnCl 2 -catalyzed transesterification with 2-pyridinemethanol ( 2 - 36 ) to form the activated palmitic ester ( 2 - 37 ) in 67% yield. Subsequent decarbonylation using Ru 3 (CO) 12 and tricyclohexylphosphine (PCy 3 ) ligand provided a mixture of olefin products in up to 95% yield.…”

Section: Feedstocksmentioning

confidence: 99%

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Defining the Macromolecules of Tomorrow through Synergistic Sustainable Polymer Research

et al. 2022

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Transforming how plastics are made, unmade, and remade through innovative research and diverse partnerships that together foster environmental stewardship is critically important to a sustainable future. Designing, preparing, and implementing polymers derived from renewable resources for a wide range of advanced applications that promote future economic development, energy efficiency, and environmental sustainability are all central to these efforts. In this Chemical Reviews contribution, we take a comprehensive, integrated approach to summarize important and impactful contributions to this broad research arena. The Review highlights signature accomplishments across a broad research portfolio and is organized into four wide-ranging research themes that address the topic in a comprehensive manner: Feedstocks, Polymerization Processes and Techniques, Intended Use, and End of Use. We emphasize those successes that benefitted from collaborative engagements across disciplinary lines.

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Section: Feedstocksmentioning

confidence: 99%

Section: Feedstocksmentioning

confidence: 99%

Defining the Macromolecules of Tomorrow through Synergistic Sustainable Polymer Research

et al. 2022

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“…In subsequent studies, a dual-catalytic directing group strategy for dehydrative decarbonylation of fatty acid methyl esters 157 (FAMEs) was reported by LaPointe, Tolman, et al (Scheme 63). 184 In this process, a Lewis acid (ZnCl 2 ) was used to catalyze transesterification to produce the corresponding esters 158, comprising a pyridine-2-methylene directing group. These were then bound to the Ru catalyst to facilitate the oxidative addition of the acyl C−O bond, while subsequent decarbonylation and β-H elimination resulted in a mixture of olefin products 159.…”

Section: Decarbonylation With Cleavage Of the C(acyl)−o/c(acyl)−c Bondsmentioning

confidence: 99%

Selective Decarbonylation via Transition-Metal-Catalyzed Carbon–Carbon Bond Cleavage

et al. 2020

Chem. Rev.

203

123

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Transition-metal-catalyzed decarbonylation via carbon−carbon bond cleavage is an essential synthetic methodology. Given the ubiquity of carbonyl compounds, the selective decarbonylative process offers a distinct synthetic strategy using carbonyl groups as "traceless handles". This reaction has been significantly developed in recent years in many respects, including catalytic system development, mechanistic understanding, substrate scope, and application in the synthesis of complex functional molecules. Therefore, this review aims to summarize the recent progress on transition-metal-catalyzed decarbonylative process, from the discovery of new transformations to the understanding of reaction mechanisms, to reveal the great achievements and potentials in this field. The contents of this review are categorized by the type of chemical bond cleavage in the decarbonylative process. The main challenges and opportunities of the decarbonylative process are also examined with the goal of expanding the application range of decarbonylation reactions.

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“…52 They also applied this methodology on fatty acids to form linear α-olefins achieving high ester conversions (>90%) and selectivities (>98%) at 190 °C. 53 However, the preparation of alkenes by the demethoxycarbonylation of methyl esters is not known.…”

Section: ■ Introductionmentioning

confidence: 99%

Conversion of Biomass-Derived Methyl Levulinate to Methyl Vinyl Ketone

Ouahabi

Smit

Angelici

et al. 2022

ACS Sustainable Chem. Eng.

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A high-throughput screening exercise testing 60 different catalysts resulted in 5 wt % Pt on sulfided carbon as the best catalyst in the conversion of bio-based methyl levulinate (ML) to methyl vinyl ketone (MVK) in a gas-phase continuous process. Up to 18% yield of MVK was obtained, but fast catalyst deactivation was observed. For a better understanding of the reaction mechanism, the potential reaction intermediates [α-angelica lactone (α-AL), γ-valerolactone, methyl ethyl ketone (MEK), and levulinic acid (LA)] were also fed as starting materials under the same reaction conditions as those used for ML. Of the different pathways possible, the route via AL seems to be the most likely route. Since the side product methanol led to the hydrogenation of MVK to MEK, LA is a better substrate in this reaction toward MVK at a medium reaction temperature. Herein, we report the highest yield of MVK (>50%) from LA at 350 °C. However, this knowledge of the reaction pathway via AL also opened up the possibility of a high-temperature conversion process of ML to MVK. It was found that ML could be converted to MVK in 71% selectivity at 600 °C using 40% CaO on γ-Al2O3 as the catalyst. Here, the catalyst merely serves to accelerate the ring closure of ML to AL, which undergoes an electrocyclic reaction under extrusion of CO to form MVK.

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Dual-catalytic decarbonylation of fatty acid methyl esters to form olefins

Cited by 14 publications

References 43 publications

Defining the Macromolecules of Tomorrow through Synergistic Sustainable Polymer Research

Defining the Macromolecules of Tomorrow through Synergistic Sustainable Polymer Research

Selective Decarbonylation via Transition-Metal-Catalyzed Carbon–Carbon Bond Cleavage

Conversion of Biomass-Derived Methyl Levulinate to Methyl Vinyl Ketone

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