Mid Sweden University

The ability of intermolecular cooperative thiourea/oxime hydrogen-bond catalysis for improving and accelerating asymmetric aminocatalysis is presented. The two readily available hydrogen-bond-donating catalysts operates in synergy with a chiral amine catalyst to accomplish highly stereoselective transformations. The synergistic catalyst systems simultaneously activate both electrophiles and nucleophiles, and make the transformations more chemo- and stereoselective. This was exemplified by performing co-catalytic enantioselective direct intermolecular α-alkylation reactions of aldehydes, direct aldol reactions, and asymmetric conjugate reactions, which gave the corresponding products in high yields and enantiomeric ratios.

We herein report that supported copper nanoparticles (CuNPs) on commercially available controlled pore glass (CPG), which exhibit high mechanical, thermal and chemical stability as compared to other silica-based materials, serve as a useful heterogeneous catalyst system for 1,3-dipolar cycloadditions (“click” reactions) between terminal alkynes and organic azides under green chemistry conditions. The supported CuNPs-CPG catalyst exhibited a broad substrate scope and gave the corresponding triazole products in high yields. The CuNPs-CPG catalyst exhibit recyclability and could be reuced multiple times without contaminating the products with Cu. 

A sustainable strategy for the neat production and surface functionalization of nanocellulose from wood pulp is disclosed. It is based on the combination of organocatalysis and click chemistry ("organoclick" chemistry) and starts with nanocellulose production by organic acid catalyzed hydrolysis and esterification of the pulp under neat conditions followed by homogenization. This nanocellulose fabrication route is scalable, reduces energy consumption and the organic acid can be efficiently recycled. Next, the surface is catalytically engineered by "organoclick" chemistry, which allows for selective and versatile attachment of different organic molecules (e.g. fluorescent probes, catalyst and pharmaceuticals). It also enables binding of metal ions and nanoparticles. This was exemplified by the fabrication of a heterogeneous nanocellulose-palladium nanoparticle catalyst, which is used for Suzuki cross-coupling transformations in water. The disclosed surface functionalization methodology is broad in scope and applicable to different nanocelluloses and cellulose based materials as well.

Herein, we report on the facile synthesis of a heterogeneous copper nanocatalyst and its combination with 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) for the aerobic oxidation of alcohols to their corresponding carbonyl compounds. This low cost copper nanocatalyst was found to exhibit excellent recyclability, making it a highly attractive catalytic system from an economical and environmental point of view. Extensive characterization of the catalyst by a number of techniques revealed that it was comprised of well-dispersed Cu(I/II) nanoparticles with an average size of around 6nm.

We report a facile in situ synthesis of spherical copper nanoparticles (NPs) templated by a gelled cellulose II matrix under alkaline aqueous reaction conditions. In under 20 min, the hybrid material could be obtained in a one-pot reaction. Field-emission scanning electron microscopy (FE-SEM) revealed that the polycrystalline NPs of 200–500 nm were well distributed in the regenerated cellulose matrix. The average Cu crystallite size was of the order of 20 nm, as estimated from both X-ray diffraction (XRD) and FE-SEM. XRD data also indicated that the composite contained up to approximately 20% Cu₂O. In suspensions containing the hybrid material, growth of Escerichia coli and Staphylococcus aureus strains was inhibited by 80% and 95%, respectively, after 72 h. The synthesis procedure offers a general approach to designing various low-cost hybrid materials of almost any shape, and the concept could be extended to utilization areas such as catalysis, functional textiles, and food packaging as well as to electronic applications.

The highly enantioselective (up to >99.5:0.5 er) synthesis of polysubstituted spirocyclic oxindoles with four new contiguous stereocenters, including the spiro all-carbon quaternary center, is disclosed. It is accomplished by the highly stereoselective control of a dynamic conjugate/intramolecular allylic alkylation relay sequence based on the synergistic cooperation of metal and chiral amine catalysts in which the careful selection of organic Nand, metal complex, and chiral amine is essential. The intermolecular C-C bond-forming step occurred only when both the metal and chiral amine catalysts were present.

In this study, lightweight biobased foamed materials were successfully synthesized by the modification of renewable polysaccharides, such as starch and microcrystalline cellulose. Low-cost and nontoxic organic acids were utilized as catalysts in the first-step esterification reaction of the synthesis. The effects of different reaction conditions on the water absorbency and weight loss of freeze-casted polysaccharide–citrate–chitosan foams are discussed. Physical properties, such as pore-size distributions and compressive stress–strain curves, of the foams were determined. The characterization results show that the amide bonds formed between the carboxylic acid groups of polysaccharide–citrate and the amino groups of chitosan are crucial to the foamed material’s performance.

Polysubstituted 5- and 6-membered carbocycles were synthesized by the title reaction. The one-pot dynamic relay process generates four new stereocenters, including a quaternary carbon center, in a highly enantioselective fashion (99.5:0.5→99:0.5 e.r.) by using a simple combination of palladium and chiral amine co-catalysts.