Polymers Based on Cyclic Carbonates as Trait d'Union Between Polymer Chemistry and Sustainable CO₂ Utilization

ChemSusChem, Journal Year: 2018, Volume and Issue: 12(4), P. 724 - 754

Published: Dec. 19, 2018

Abstract Given the large amount of anthropogenic CO 2 emissions, it is advantageous to use as feedstock for fabrication everyday products, such fuels and materials. An attractive way in synthesis polymers by formation five‐membered cyclic organic carbonate monomers (5CCs). The sustainability this synthetic approach increased using scaffolds prepared from renewable resources. Indeed, recent years have seen rise various types syntheses applications. 5CC are often polymerized with diamines yield polyhydroxyurethanes (PHU). Foams developed type polymers; moreover, additional hydroxyl groups PHU, absent classical polyurethanes, lead coatings excellent adhesive properties. Furthermore, offer possibility post‐functionalization, curing reactions under mild conditions. Finally, polarity remarkably high, so carbonates side‐chains can be used polymer electrolytes batteries or conductive membranes. target Review highlight multiple opportunities offered and/or containing 5CCs. Firstly, preparation several classes 5CCs discussed special focus on routes. Thereafter, specific which presence moieties crucial impart targeted properties (foams, adhesives, energy applications, other functional materials).

Language: Английский

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Recent progress in the catalytic transformation of carbon dioxide into biosourced organic carbonates

Green Chemistry, Journal Year: 2021, Volume and Issue: 23(3), P. 1077 - 1113

Published: Jan. 1, 2021

The recent advances made in the catalytic preparation of biobased cyclic carbonates derived from sugars, glycerol, fatty acids/vegetable oils and terpenes are presented, together with a discussion surrounding their potential applications.

Language: Английский

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Recent advances in the use of catalysts based on natural products for the conversion of CO₂into cyclic carbonates

Green Chemistry, Journal Year: 2020, Volume and Issue: 22(22), P. 7665 - 7706

Published: Jan. 1, 2020

In this review we present a structured overview of the chemical catalytic systems containing any component derived from natural product for cycloaddition carbon dioxide to epoxides form cyclic carbonates.

Language: Английский

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Advances in Palladium‐Catalyzed Decarboxylative Cycloadditions of Cyclic Carbonates, Carbamates and Lactones

ChemCatChem, Journal Year: 2022, Volume and Issue: 14(9)

Published: Jan. 31, 2022

Abstract Palladium‐catalyzed decarboxylative cycloadditions have emerged as highly effective methods for constructing structurally diverse carbo‐ and heterocycles because of the formation at least two carbon‐carbon or carbon‐heteroatom bonds in a single step. It is great interest to chemists that this type cycloaddition reactions possesses some special advantages such high reactivity, exclusive regioselectivity, good functional group compatibility. Based on these qualities, palladium‐catalyzed present strong ability synthetic chemistry been flourished especially last five years. In review, achievements involving cyclic carbonates, carbamates, lactones accessing oxacyclo‐, azacyclo‐ carbocyclic compounds are addressed. Mechanistic insights applications toward synthesis natural products discussed. The challenges opportunities field also outlined.

Language: Английский

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Interrupting Associative π–σ–π Isomerization Enables Z-Retentive Asymmetric Tsuji–Trost Reaction

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(3), P. 2776 - 2785

Published: Jan. 8, 2025

The asymmetric Tsuji-Trost reaction has been extensively studied due to its importance in establishing stereogenic centers, often adjacent an E-olefin moiety organic molecules. generally preferential formation of chiral products is believed result from the thermodynamically more stable syn-π-allylpalladium intermediate. rapid associative π-σ-π isomerization makes it challenging synthesize Z-olefin via transient anti-π-allylpalladium Herein, we report a strategy for regulating by tuning steric bulkiness ligands, allylic leaving groups, and counteranions. utilization Pd catalyst derived phosphoramidite ligands interrupts isomerization, enabling highly efficient Z-retentive toward array α-amino acid derivatives bearing motif high yields (up 95%) excellent stereoselectivity 99% ee >19:1 Z/E) with low loading (0.1 mol %). mechanistic insights design reported this work pave way rational developments Tsuji-Trost-type reactions.

Language: Английский

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Current advances in the catalytic conversion of carbon dioxide by molecular catalysts: an update

Dalton Transactions, Journal Year: 2018, Volume and Issue: 47(38), P. 13281 - 13313

Published: Jan. 1, 2018

Due to the high emissions of CO2 and related environmental impact, chemical transformation useful industrially relevant products or their precursor is significant interest. Recycling as a building block for synthesis chemicals may not only reduce further emission by at least replacing oil-derived feedstocks, but also provide advantages an inexpensive, non-toxic easily available substrate. The catalytic conversion into small, molecules such carbonates, methyl amines, methanol, formic acid, etc. molecular catalysts interesting topic that has strongly developed in recent years. This review provides overview current scientific progress activation carbon dioxide with scientifically substrates using catalysts. Metal-based are presented first part whereas metal-free systems described second part.

Language: Английский

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Copper‐Catalyzed Enantioselective Construction of Tertiary Propargylic Sulfones

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(12), P. 3903 - 3907

Published: Jan. 21, 2019

Tertiary propargylic sulfones are of significant importance in organic synthesis and medicinal chemistry, but to date no general asymmetric approach has been developed. We disclose a versatile copper-catalyzed sulfonylation cyclic carbonates using sodium sulfinates that allows the construction featuring elusive quaternary stereocenters. This method provides first successful example such an enantioselective sulfonylation, features high induction, wide functional group tolerance, scalability, enables attractive product diversification.

Language: Английский

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Regiodivergent construction of medium-sized heterocycles from vinylethylene carbonates and allylidenemalononitriles

Chemical Science, Journal Year: 2020, Volume and Issue: 11(11), P. 2888 - 2894

Published: Jan. 1, 2020

Here we report palladium-catalyzed, regiodivergent [5 + 4] and 2] annulations of vinylethylene carbonates allylidenemalononitriles affording over 50 medium-sized heterocycles in high isolated yields with excellent regioselectivities.

Language: Английский

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Assessing the pK_a‐Dependent Activity of Hydroxyl Hydrogen Bond Donors in the Organocatalyzed Cycloaddition of Carbon Dioxide to Epoxides: Experimental and Theoretical Study

Advanced Synthesis & Catalysis, Journal Year: 2018, Volume and Issue: 361(2), P. 366 - 373

Published: Oct. 29, 2018

Abstract The development of hydrogen bond donors (HBDs) as catalytic moieties in the cycloaddition carbon dioxide to epoxides is an active field research access efficient, inexpensive and sustainable metal‐free systems for conversion useful chemicals. Thus far, no systematic attempt correlate activity a diverse selection HBDs their physico‐chemical properties has been undertaken. In this work, we investigate factors influencing hydroxyl from different chemical families under ambient conditions by considering Brønsted acidity (expressed pK ), number hydroxyls structural aspects. As effect, study highlights crucial role protons’ determining HBDs, identifies ideal range proton (9 <pK <11) leads revaluation phenol discovery simple ascorbic acid derivative efficient title reaction. Density functional theory (DFT) calculations show mild reactions barriers reaction catalysed suggest occurrence aggregation between molecules further factor affecting activity. magnified image

Language: Английский

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Palladium‐Catalyzed Asymmetric [8+2] Dipolar Cycloadditions of Vinyl Carbamates and Photogenerated Ketenes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(33), P. 14096 - 14100

Published: May 6, 2020

Higher-order cycloadditions, particularly [8+2] are a straightforward and efficient strategy for constructing significant medium-sized architectures. Typically, configuration-restrained conjugated systems utilized as 8π-components higher-order concerted cycloadditions. However, this reason, 10-membered monocyclic skeletons have never been constructed via catalytic asymmetric cycloaddition with high peri- stereoselectivity. Here, we accomplished an enantioselective dipolar the merger of visible-light activation palladium catalysis. This protocol provides new route to architectures bearing chiral quaternary stereocenters chemo-, peri-, enantioselectivity. The success relied on facile in situ generation Pd-containing 1,8-dipoles their trapping by ketene dipolarophiles, which were formed photo-Wolff rearrangement.

Language: Английский

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