RESUMEN

CO2-based aliphatic polycarbonates (aPCs), produced through the alternating copolymerization of epoxides with CO2, present an appealing option for sustainable polymeric materials owing to their renewable feedstock and degradable characteristics. An ongoing challenge in working with aPCs is modifying their mechanical properties to meet specific demands. Herein, we report that monomer ratio and polymer architecture of aPCs impact not only printability by digital light processing (DLP) additive manufacturing, but also dictate the thermomechanical and degradation properties of the printed objects. We found that block copolymers exhibit tailorable thermomechanical properties ranging from soft elastomeric to strong and brittle as the proportion of hard blocks increases, whereas the homopolymer blend failed to print objects and statistical copolymers delaminated or overcured, displaying the weakest mechanical properties. In addition, the hydrolytic degradation of the prints was demonstrated under various conditions, revealing that BCP prints containing a higher proportion of hard blocks had slower degradation and that statistical copolymer prints degraded more slowly than their BCP counterparts. This study underscores that polymer composition and architecture both play key roles in resin printability and bulk properties, offering significant prospects for advancing sustainable materials in additive manufacturing through polymer design.

RESUMEN

Metallosurfactants, defined here as hydrophobic metal-containing groups embedded in hydrophilic units when dispersed in water, emanate in the formation of metallomicelles. This approach continues to attract great interest for its ability to serve as micellar catalysts for various metal-mediated chemical transformations in water. Indeed, relevant to green chemistry, micellar catalysis plays a preeminent function as a replacement for organic solvents in a variety of chemical reactions. There are several methods for the interaction of metal complexes (catalysts or catalyst precursors) and surfactants for producing micellar aggregates. A very effective manner for achieving this involves the direct bonding of the metal center to the amphiphilic polymeric materials. Herein, we describe the synthesis of a metallosurfactant containing a palladium complex covalently incorporated into a CO2-based triblock polycarbonate derived using a dicarboxylic acid chain-transfer agent. This amphiphilic polycarbonate was shown to self-assemble in water to provide uniform and spherical micelles, where the catalytic metal center is located in the hydrophobic portion of the micelle. The resulting metallosurfactant was demonstrated to effectively catalyze carbon-carbon coupling reactions at very low catalyst loadings.

RESUMEN

Recent years have witnessed intensive research activity in exploring novel metal-free organocatalysts for catalyzing the coupling reactions of CO2 and epoxides to afford cyclic or polymeric carbonates. In this direction, herein we report a series of boron-phosphonium organocatalysts for catalyzing the coupling reactions of CO2 and epoxides. These organophosphonium catalysts were synthesized in high yields by following a two step protocol involving Menschutkin and hydroboration reactions in succession. The purity of these organocatalysts was confirmed by spectroscopic techniques like 1H, 13C and 31P NMR, and molecular structures were confirmed by single crystal X-ray diffraction studies. We have also demonstrated that these bifunctional organoboron-phosphonium catalysts are comparatively much less hygroscopic compared to the analogus ammonium catalysts. These phosphonium organocatalysts were shown to catalyze the copolymerization of CO2 and cyclohexene oxide or vinyl cyclohexene oxide to provide polycarbonates with >99% polymer selectivity and carbonate linkages. The coupling reactions of aliphatic epoxides such as PO, having lower energy barrier to cycloaddition formation compared to alicyclic epoxides, preferentially provided cyclic carbonates in good yields. It was demonstrated that these organoboron-phosphonium catalysts are sensitive to chain transfer agents like water, and hence are deactivated in its presence. This is opposite to what is observed for metal based catalysts for these transformations, where water serves as a precursor to the chain-transfer agent diols.

RESUMEN

Oxazolidinone synthesis through the coupling of carbon dioxide and aziridines was catalysed by an aluminium(salphen) complex at 50-100 °C and 1-10 bar pressure under solvent-free conditions. The process was applicable to a variety of substituted aziridines, giving products with high regioselectivity. It involved the use of a sustainable and reusable aluminium-based catalyst, used carbon dioxide as a C1 source and provided access to pharmaceutically important oxazolidinones as illustrated by a total synthesis of toloxatone. This protocol was scalable, and the catalyst could be recovered and reused. A catalytic cycle was proposed based on stereochemical, kinetic and Hammett studies.

RESUMEN

Copper efficiently catalyzed nucleophilic ring opening, sp3 C-H functionalization, and C-N bond formation in the presence of tert-butyl hydroperoxide to afford functionalized imidazolidines starting from N-sulfonylaziridines and N-alkylanilines. The products were obtained in high optical purities (95 → 99% ee) with excellent functional group tolerance.

RESUMEN

An Al(salen)Cl efficiently catalyzed the enantiospecific (3+2) cycloaddition of unactivated chiral aziridines with isothiocyanates to furnish functionalized iminothiazolidines at room temperature with 94-99% ee. The use of an aluminum Lewis acid as the catalyst, high enantiomeric purities, mild reaction conditions, broad substrate scope, and the high atom economy are the significant practical features.

RESUMEN

On water oxidative C(sp3)-H functionalization/C-O/C-N bonds formations using tetrabutylammonium iodide as the catalyst and tert-butyl hydroperoxide in water (T-Hydro) as the oxidant affords a potential route for the construction of functionalized oxazolidines and imidazolidines. The reaction is simple, regioselective, and effective at moderate temperature with broad substrate scope. In the case of optically active substrates, the oxidative cyclization can be accomplished with high optical purities.

RESUMEN

Various tetrasubstituted pyrroles/pyrazoles have been prepared from nitro-substituted 1,3-enynes with aromatic amines/hydrazines via a copper-catalyzed cascade aza-Michael addition, cyclization and aromatization at room temperature. This protocol is also effective for the synthesis of tetrasubstituted pyrazoles in high yields.

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RESUMEN

The synthesis of pentasubstituted pyrroles has been described using molecular iodine from 1,3-enynes and amines via a sequential tandem aza-Michael addition, iodocyclization, and oxidative aromatization. The protocol is simple and efficient to afford the target products at ambient conditions.

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RESUMEN

In suspension: the reaction of aziridines with heterocumulenes in the presence of Fe(NO(3))(3)⋅9H(2)O in aqueous suspension provides access to functionalized five-membered heterocycles in good to high yields. This protocol has a wide substrate scope, is simple, and uses a nontoxic and cheap catalyst.

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