Direct Synthesis of an α,ω‐Diester from 2,7‐Octadienol as Bulk Feedstock in Three Tandem Catalytic Steps

Ostrowski, Karoline A.; Vogelsang, Dennis; Seidensticker, Thomas; Vorholt, Andreas J.

doi:10.1002/chem.201503785

Cited by 14 publications

(17 citation statements)

References 42 publications

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“…Tandem catalyses are a hot topic in catalytic carbonylation reactions when it comes to increasing the efficiency of chemical processes, because it makes merging different reaction steps into a single preparative step possible, reducing waste while saving time and energy . Transition metal catalyzed tandem catalyses often involve hydroformylation as the initial reaction step to form reactive aldehydes , which constitutes a well investigated reaction that is also the subject ongoing research .…”

Section: Introductionmentioning

confidence: 99%

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Vorholt

Immohr

Ostrowski

et al. 2016

Euro J Lipid Sci & Tech

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This article describes the development of an effective thermomorphic multicomponent solvent (TMS) system for the production of branched polyamide monomers. In this system, methyl oleate, a renewable from fats and oils, and a functionalized amine are used as starting materials in a tandem catalytic reaction, which merges different reaction steps into a single preparative step. This particular TMS system consisted of a heptane/acetonitrile solvent mixture and made reusing the precious rhodium catalyst possible in three recycle runs. A constant yield of 61–65% was obtained for each run due to low‐catalyst leaching. Fortunately, the catalyst system does not require any additional phosphorous ligands and allows high yields. A scale‐up for the production of 10–11 g of the desired product in each run was realized. Subsequent hydrogenation of the product directly provided an amine ester, which is a valuable polyamide monomer. Practical applications: A method was developed to enable access to primary amines via hydroaminomethylation and hydrogenation. The product, a nitrile ester, is a valuable intermediate for polyamide monomers. This nitrile ester was successfully hydrogenated to an amine ester, which features a potential polyamide monomer directly. A catalyst recycle of the homogeneous rhodium complex within the hydroaminomethylation of methyl oleate and an amino nitrile was successfully carried out, enabling constant homogeneous catalyst activity over the course of three recycle runs. A scale‐up to obtain 10–11 g of the hydroaminomethylation product was realized. A general method is described for the conversion of methyl oleate within a hydroaminomethylation reaction. The catalyst can be recovered and reused. Valuable polyamide intermediates were obtained.

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Section: Introductionmentioning

confidence: 99%

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Vorholt

Immohr

Ostrowski

et al. 2016

Euro J Lipid Sci & Tech

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“…Our working group reported on a tandem reaction sequence, which does not require such complicated isolation and purification steps of the intermediate products in order to produce a valuable polymer precursor . In a single preparative step, a yield of up to 64 % of a linear C10‐diester compound is achieved using a single, distinct palladium catalyst for each of the three required individual tandem reaction steps (Figure ).…”

Section: C4 Moleculesmentioning

confidence: 99%

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

et al. 2018

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For many years, the efficient use of resources has been a major and permanent challenge for the chemical industry. The implementation of alternative resources such as renewables and carbon dioxide has been a subject of considerable discussion, but also the more efficient use of long known bulk chemicals is of great interest. Among them, 1,3‐dienes such as 1,3‐butadiene from the C4 cut of the naphtha cracker as well as isoprene, piperylene and cyclopentadiene from the corresponding C5 section are important substrates. These dienes are presently employed in various markets, with the greatest importance being in the production of polymers and copolymers. However, homogeneous transition metal catalysis has proven to be a versatile tool to functionalize these important 1,3‐dienes to low molecular weight fine chemicals by introducing, for example, nitrogen, oxygen or silicon. Hence, an upgraded use of the corresponding products as agrochemicals, pharmaceuticals, fragrances or special detergents is close at hand. The main approaches in the topic of homogeneous functionalization reactions of the industrially relevant 1,3‐dienes will be summarized and discussed within the present article. Besides that, novel applications including renewable 1,3‐dienes, for example β‐myrcene and β‐farnesene, as well as the application of CO2 in telomerization, will be critically discussed.

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“…[1][2][3] Besides the direct insertion of carbon monoxide into, for instance, alcohols yielding carboxylic acids or into allylic substrates such as alcohols, [4][5][6] ethers [7] and amines [8] yielding the corresponding unsaturated carboxylic acid derivatives, the carbonylation of unsatured substrates including the addition of a brønstedt-acidic nucleophiles is a powerful tool. Principally, high catalyst activities and excellent selectivities can be reached due to the defined catalyst structure, contributing to highly atom economic reactions, as e. g. manifested for palladium catalysed carbonylation reactions.…”

Section: Introductionmentioning

confidence: 99%

Palladium Catalysed Acid‐Free Carboxytelomerisation of 1,3‐Butadiene with Alcohols Accessing Pelargonic Acid Derivatives Including Triglycerides under Selectivity Control

et al. 2019

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Palladium catalysed carboxytelomerisation of 1,3-butadiene with alcohols yields unsaturated C 9 -pelargonic esters in an atom-economic and straightforward way. Although carboxytelomerisation is of current interest, limitations of applicable alcohol substrates have not been fully investigated. In here, we present the transfer of the catalytic system comprising palladium acetate and tri-n-butyl phosphine in pyridine to a broad variety of 20 alcohols with vast difference in nucleophilicity and sterical demands yielding the corresponding esters in a 100% atom economic manner. Effects of nucleophilicity and sterical demands were revealed for monoalcohols, di-and polyols. Whilst yields, chemoselectivity and E/Z-selectivity of the pelargonic acid derivatives were excellent with up to 99%, selectivity towards mono-, di-and triesters could be controlled successfully. Finally, the reaction profile of the carboxytelomerisation glycerol was uncovered, yielding up to 97% of industrially relevant unsaturated C 9 -short chain fats.

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Direct Synthesis of an α,ω‐Diester from 2,7‐Octadienol as Bulk Feedstock in Three Tandem Catalytic Steps

Cited by 14 publications

References 42 publications

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

Palladium Catalysed Acid‐Free Carboxytelomerisation of 1,3‐Butadiene with Alcohols Accessing Pelargonic Acid Derivatives Including Triglycerides under Selectivity Control

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