Novel synthesis routes for the preparation of low toxic vinyl ester and vinyl carbonate monomers

Hofecker, Andreas; Knaack, Patrick; Steinbauer, Patrick; Markovic, Marica; Ovsianikov, Aleksandr; Liska, Robert

doi:10.1080/00397911.2020.1808995

Cited by 3 publications

(4 citation statements)

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“…Mechanism of Transvinylation. For the palladium(II)chloride-catalyzed vinyl transfer reaction, we propose a mechanism with Pd-enolate 14 as the key intermediate (Scheme 5), analogous to a mechanism proposed by Hoefecker et al 48 The acetaldehyde anion is carbon-bound to Pd(II), 49 similar to the analogous mercury compounds, which also have been used in vinyl transfer reactions. 50 The reaction starts with the nucleophilic attack of a chloride ion to silicon and subsequent coordination of the enolate (Scheme 5).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Exceptionally Mild and High-Yielding Synthesis of Vinyl Esters of Alpha-Ketocarboxylic Acids, Including Vinyl Pyruvate, for Parahydrogen-Enhanced Metabolic Spectroscopy and Imaging

Brahms,

Pravdivtsev,

Thorns

et al. 2023

J. Org. Chem.

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Metabolic changes often occur long before pathologies manifest and treatment becomes challenging. As key elements of energy metabolism, α-ketocarboxylic acids (α-KCA) are particularly interesting, e.g., as the upregulation of pyruvate to lactate conversion is a hallmark of cancer (Warburg effect). Magnetic resonance imaging with hyperpolarized metabolites has enabled imaging of this effect non-invasively and in vivo, allowing the early detection of cancerous tissue and its treatment. Hyperpolarization by means of dynamic nuclear polarization, however, is complex, slow, and expensive, while available precursors often limit parahydrogen-based alternatives. Here, we report the synthesis for novel 13C, deuterated ketocarboxylic acids, and a much-improved synthesis of 1-13C-vinyl pruvate-d6, arguably the most promising tracer for hyperpolarizing pyruvate using parahydrogen-induced hyperpolarization by side arm hydrogenation. The new synthesis is scalable and provides a high yield of 52%. We elucidated the mechanism of our Pd-catalyzed trans-vinylation reaction. Hydrogenation with parahydrogen allowed us to monitor the addition, which was found to depend on the electron demand of the vinyl ester. Electron-poor α-keto vinyl esters react slower than “normal” alkyl vinyl esters. This synthesis of 13C, deuterated α-ketocarboxylic acids opens up an entirely new class of biomolecules for fast and cost-efficient hyperpolarization with parahydrogen and their use for metabolic imaging.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Exceptionally Mild and High-Yielding Synthesis of Vinyl Esters of Alpha-Ketocarboxylic Acids, Including Vinyl Pyruvate, for Parahydrogen-Enhanced Metabolic Spectroscopy and Imaging

Brahms,

Pravdivtsev,

Thorns

et al. 2023

J. Org. Chem.

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“…[14] In particular, Liska et al reported the synthesis of vinyl esters through the reaction of acyl chlorides and a simple enol silyl ether, trimethyl(vinyloxy)silane, in the presence of KF and 18-crown-6. [15] In this case, however, a sort of acyl chlorides employed was limited to a few cases and excess amounts of KF were used.…”

Section: Introductionmentioning

confidence: 99%

Selective O‐Acylation of Enol Silyl Ethers with Acyl Fluorides Catalyzed by Fluoride Ions Derived from Potassium Fluoride and 18‐Crown‐6

Sakai,

Watanabe,

Mori

et al. 2024

ChemistryOpen

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“…14 These multistep reactions are atom inefficient and cost intensive. Previously, Hofecker et al 15 reported a more convenient, more economic and safer synthesis pathway to obtain VEs in sufficient yields. VE homopolymers are very brittle and often break during crosslinking due to high shrinkage stress.…”

Section: Introductionmentioning

confidence: 99%

“…These multistep reactions are atom inefficient and cost intensive. Previously, Hofecker et al 15 . reported a more convenient, more economic and safer synthesis pathway to obtain VEs in sufficient yields.…”

Section: Introductionmentioning

confidence: 99%

Approaching new biomaterials: copolymerization characteristics of vinyl esters with norbornenes, allyl esters and allyl ethers

Steinbauer

Liska

Baudis

2021

Polymer International

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Vinyl ester‐based monomers for radical photopolymerization have recently been shown to be promising alternatives to (meth)acrylates through lower irritancy and cytotoxicity. Vinyl ester monomers are becoming increasingly important on account of new, more cost‐efficient synthetic production methods, not to forget their increased reactivity and improved material properties in combination with thiol–ene polymerization. Due to their biocompatibility and degradability, these monomers are more frequently used in tissue engineering. Nevertheless, the material properties can be improved by possible copolymerizations with other monomers. Therefore, the copolymerization behavior of vinyl ester with norbornene, allyl ether and allyl ester has been studied fundamentally in a photoreactor via free radical photopolymerization. Here, the consumption of double bonds of the monomers has been identified using NMR spectroscopy. Copolymerization parameters have been determined using the Kelen–Tüdös method. Results show equal consumption of vinyl ester and co‐monomer double bonds leading to alternating copolymerizations. The double bond conversion was confirmed via in situ real‐time near‐infrared photorheology. Mono‐ and difunctional vinyl esters with co‐monomers have also provided further insight into the polymer network of these copolymers. © 2021 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.

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Novel synthesis routes for the preparation of low toxic vinyl ester and vinyl carbonate monomers

Abstract: Liska (2020): Novel synthesis routes for the preparation of low toxic vinyl ester and vinyl carbonate monomers, Synthetic Communications,

Cited by 3 publications

References 32 publications

Exceptionally Mild and High-Yielding Synthesis of Vinyl Esters of Alpha-Ketocarboxylic Acids, Including Vinyl Pyruvate, for Parahydrogen-Enhanced Metabolic Spectroscopy and Imaging

Exceptionally Mild and High-Yielding Synthesis of Vinyl Esters of Alpha-Ketocarboxylic Acids, Including Vinyl Pyruvate, for Parahydrogen-Enhanced Metabolic Spectroscopy and Imaging

Selective O‐Acylation of Enol Silyl Ethers with Acyl Fluorides Catalyzed by Fluoride Ions Derived from Potassium Fluoride and 18‐Crown‐6

Approaching new biomaterials: copolymerization characteristics of vinyl esters with norbornenes, allyl esters and allyl ethers

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