Extending the chemical product tree: a novel value chain for the production of <i>N</i>-vinyl-2-pyrrolidones from biogenic acids

Haus, Moritz O.; Louven, Yannik; Palkovits, Regina

doi:10.1039/c9gc01488h

Cited by 14 publications

(20 citation statements)

References 34 publications

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“…Among them, HEP in combination with TMG showed the best performance in terms of reaction time and yield. HEP is a biogenic solvent [26] that is already available in large quantities, being an intermediate for the synthesis of N ‐vinyl‐pyrrolidone. In addition to its excellent dissolution capacity, HEP has a very high affinity for water that allows a smooth product extraction during work up, using standard organic solvents.…”

Section: Resultsmentioning

confidence: 99%

Palladium Catalyst Recycling for Heck‐Cassar‐Sonogashira Cross‐Coupling Reactions in Green Solvent/Base Blend

et al. 2021

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The identification of a green, versatile, user‐friendly, and efficient methodology is necessary to facilitate the use of Heck‐Cassar‐Sonogashira (HCS) cross‐coupling reaction in drug discovery and industrial production in the pharmaceutical segment. The Heck‐Cassar and Sonogashira protocols, using N‐hydroxyethylpyrrolidone (HEP)/water/N,N,N′,N′‐tetramethyl guanidine (TMG) as green solvent/base mixture and sulfonated phosphine ligands, allowed to recycle the catalyst, always guaranteeing high yields and fast conversion under mild conditions, with aryl iodides, bromides, and triflates. No catalyst leakage or metal contamination of the final product were observed during the HCS recycling. To our knowledge, a turnover number (TON) up to 2375, a turnover frequency (TOF) of 158 h−1, and a process mass intensity (PMI) around 7 that decreased around 3 after solvent, base, and palladium recovery, represent one of the best results to date using a sustainable protocol. The Heck‐Cassar protocol using sSPhos was successfully applied to the telescoped synthesis of Erlotinib (TON: 1380; TOF: 46 h−1).

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Section: Resultsmentioning

confidence: 99%

Palladium Catalyst Recycling for Heck‐Cassar‐Sonogashira Cross‐Coupling Reactions in Green Solvent/Base Blend

et al. 2021

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“…They were tested after drying and reduction according to previously established procedures. 21 In contrast, TiO 2 -supported materials were synthesized using Pt(NH 3 ) 4 (NO 3 ) 2 (Sigma-Aldrich, ≥50 wt % Pt) and NH 4 ReO 4 (ChemPur, >99.5%) as metal precursors. The support material, anatase TiO 2 (ST6*120), was provided by Saint-Gobain NorPro.…”

Section: Methodsmentioning

confidence: 99%

Correlating the Synthesis, Structure, and Catalytic Performance of Pt–Re/TiO₂ for the Aqueous-Phase Hydrogenation of Carboxylic Acid Derivatives

et al. 2021

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Pt–Re bimetallic catalysts have many applications, ranging from catalytic reforming to the reduction of carboxylic acid derivatives. However, the exact role of Re in these systems has remained a matter of discussion, partly due to the plethora of suggested synthesis protocols and analysis conditions. This study presents an extensive comparison of such literature protocols and the resulting materials. In detail, characterization by N2 physisorption, X-ray diffraction, temperature-programmed reduction, CO pulse chemisorption, Fourier-transform infrared spectroscopy of adsorbed CO, scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, and in situ X-ray photoelectron spectroscopy is combined with catalytic testing to yield synthesis–structure–activity correlations. Accordingly, the investigated catalysts share common features, such as Pt0 nanoparticles (1–4 nm) decorated with partially reduced Re species (ReO x–y ). The remaining rhenium oxide is spread over the TiO2 support and enhances Pt dispersion in sequential impregnation protocols. While differences in the number of active sites (Pt0/ReO x–y ) mostly explain catalytic results, small variations in the extent of Re reduction and site composition cause additional modulations. The optimal bimetallic catalyst outperforms Ru/C (previous benchmark) in the reduction of N-(2-hydroxyethyl)succinimide, an important step in the production of a bio-based polyvinylpyrrolidone polymer.

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“…Furthermore, HEP can be potentially very inexpensive, being an intermediate in the green synthesis of N -vinylpyrrolidone from biogenic acids. 24 …”

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confidence: 99%

“…However, HEP is a nontoxic solvent, manageable at high temperatures and easily removable by a simple workup as reported above. Furthermore, HEP can be potentially very inexpensive, being an intermediate in the green synthesis of N -vinylpyrrolidone from biogenic acids …”

mentioning

confidence: 99%

“…Furthermore, HEP can be potentially very inexpensive, being an intermediate in the green synthesis of N-vinylpyrrolidone from biogenic acids. 24 The reaction was extended to substituted aryl iodides and acetylenes (see Scheme 2 and Table 2). For each couple of substrates, the mildest conditions to reach complete conversion were investigated, starting from the best conditions identified in the model reaction between 1a and 2a.…”

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confidence: 99%

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Fast Heck–Cassar–Sonogashira (HCS) Reactions in Green Solvents

et al. 2020

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The replacement of toxic solvents with greener alternatives in Heck–Cassar–Sonogashira (HCS) cross-couplings was investigated. The fine-tuning of the HCS protocol allowed to achieve complete conversions and high speed under mild conditions. N -Hydroxyethylpyrrolidone (HEP) gave the best results. Moreover, the methodology was successfully applied to the synthesis of an intermediate of the anticancer drug Erlotinib, demonstrating the versatility of the new green protocol.

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Extending the chemical product tree: a novel value chain for the production of N-vinyl-2-pyrrolidones from biogenic acids

Abstract: Bio-based monomers are synthesized in a two-step process starting from common platform chemicals. The featured sequence of heterogeneously-catalyzed reduction and gas phase dehydration makes for a promising alternative to traditional Reppe chemistry.

Cited by 14 publications

References 34 publications

Palladium Catalyst Recycling for Heck‐Cassar‐Sonogashira Cross‐Coupling Reactions in Green Solvent/Base Blend

Palladium Catalyst Recycling for Heck‐Cassar‐Sonogashira Cross‐Coupling Reactions in Green Solvent/Base Blend

Correlating the Synthesis, Structure, and Catalytic Performance of Pt–Re/TiO₂ for the Aqueous-Phase Hydrogenation of Carboxylic Acid Derivatives

Fast Heck–Cassar–Sonogashira (HCS) Reactions in Green Solvents

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Extending the chemical product tree: a novel value chain for the production of N-vinyl-2-pyrrolidones from biogenic acids

Abstract: Bio-based monomers are synthesized in a two-step process starting from common platform chemicals. The featured sequence of heterogeneously-catalyzed reduction and gas phase dehydration makes for a promising alternative to traditional Reppe chemistry.

Cited by 14 publications

References 34 publications

Palladium Catalyst Recycling for Heck‐Cassar‐Sonogashira Cross‐Coupling Reactions in Green Solvent/Base Blend

Palladium Catalyst Recycling for Heck‐Cassar‐Sonogashira Cross‐Coupling Reactions in Green Solvent/Base Blend

Correlating the Synthesis, Structure, and Catalytic Performance of Pt–Re/TiO2 for the Aqueous-Phase Hydrogenation of Carboxylic Acid Derivatives

Fast Heck–Cassar–Sonogashira (HCS) Reactions in Green Solvents

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Correlating the Synthesis, Structure, and Catalytic Performance of Pt–Re/TiO₂ for the Aqueous-Phase Hydrogenation of Carboxylic Acid Derivatives