Regio- and Stereoselective Carbon-Boron Bond Formation via Heterogeneous Palladium-Catalyzed Hydroboration of Enallenes.

A highly efficient regio- and stereoselective heterogeneous palladium-catalyzed hydroboration reaction of enallenes was developed. Nanopalladium immobilized on microcrystalline cellulose (MCC) was successfully employed as an efficient catalyst for the enallene hydroboration reaction. The nanopalladium particles were shown by HAADF-STEM to have an average size of 2.4 nm. The cellulose-supported palladium catalyst exhibits high stability and provides vinyl boron products in good to high isolated yields (up to 90 %). The nanopalladium catalyst can be efficiently recycled and it was demonstrated that the catalyst can be used in 7 runs with a maintained high yield (>80 %). The vinylboron compounds prepared from enallenes are important synthetic intermediates that can be used in various organic synthetic transformations.

Silver-Triggered Activity of a Heterogeneous Palladium Catalyst in Oxidative Carbonylation Reactions.

A silver-triggered heterogeneous Pd-catalyzed oxidative carbonylation has been developed. This heterogeneous process exhibits high efficiency and good recyclability, and was utilized for the one-pot construction of polycyclic compounds with multiple chiral centers. AgOTf was used to remove chloride ions in the heterogeneous catalyst Pd-AmP-CNC, thereby generating highly active PdII , which results in high efficiency of the heterogeneous catalytic system.

Subtilisin integrated artificial plant cell walls as heterogeneous catalysts for asymmetric synthesis of (S)-amides.

Subtilisin integrated artificial plant-cell walls (APCWs) were fabricated by self-assembly using cellulose or nanocellulose as the main component. The resulting APCW catalysts are excellent heterogeneous catalysts for the asymmetric synthesis of (S)-amides. This was demonstrated by the APCW-catalyzed kinetic resolution of several racemic primary amines to give the corresponding (S)-amides in high yields with excellent enantioselectivity. The APCW catalyst can be recycled for multiple reaction cycles without loss of enantioselectivity. The assembled APCW catalyst was also able to cooperate with a homogeneous organoruthenium complex, which allowed for the co-catalytic dynamic kinetic resolution (DKR) of a racemic primary amine to give the corresponding (S)-amide in high yield. The APCW/Ru co-catalysis constitutes the first examples of DKR of chiral primary amines when subtilisin is used as a co-catalyst.

Cellulose-Supported Heterogeneous Gold-Catalyzed Cycloisomerization Reactions of Alkynoic Acids and Allenynamides.

Herein, we describe efficient nanogold-catalyzed cycloisomerization reactions of alkynoic acids and allenynamides to enol lactones and dihydropyrroles, respectively (the latter via an Alder-ene reaction). The gold nanoparticles were immobilized on thiol-functionalized microcrystalline cellulose and characterized by electron microscopy (HAADF-STEM) and by XPS. The thiol-stabilized gold nanoparticles (Au0) were obtained in the size range 1.5-6 nm at the cellulose surface. The robust and sustainable cellulose-supported gold nanocatalyst can be recycled for multiple cycles without losing activity.

A facile route for concurrent fabrication and surface selective functionalization of cellulose nanofibers by lactic acid mediated catalysis.

Celulose nanofibers are lightweight, recycable, biodegradable, and renewable. Hence, there is a great interest of using them instead of fossil-based components in new materials and biocomposites. In this study, we disclose an environmentally benign (green) one-step reaction approach to fabricate lactic acid ester functionalized cellulose nanofibrils from wood-derived pulp fibers in high yields. This was accomplished by converting wood-derived pulp fibers to nanofibrillated "cellulose lactate" under mild conditions using lactic acid as both the reaction media and catalyst. Thus, in parallel to the cellulose nanofibril production, concurrent lactic acid-catalyzed esterification of lactic acid to the cellulose nanofibers surface occured. The direct lactic acid esterification, which is a surface selective functionalization and reversible (de-attaching the ester groups by cleavage of the ester bonds), of the cellulose nanofibrils was confirmed by low numbers of degree of substitution, and FT-IR analyses. Thus, autocatalytic esterification and cellulose hydrolysis occurred without the need of metal based or a harsh mineral acid catalysts, which has disadvantages such as acid corrosiveness and high recovery cost of acid. Moreover, adding a mineral acid as a co-catalyst significantly decreased the yield of the nanocellulose. The lactic acid media is successfully recycled in multiple reaction cycles producing the corresponding nanocellulose fibers in high yields. The disclosed green cellulose nanofibril production route is industrial relevant and gives direct access to nanocellulose for use in variety of applications such as sustainable filaments, composites, packaging and strengthening of recycled fibers.

Efficient Heterogeneous Copper-Catalyzed Alder-Ene Reaction of Allenynamides to Pyrrolines.

Herein, we describe an efficient nanocopper-catalyzed Alder-ene reaction of allenynamides. The copper nanoparticles were immobilized on amino-functionalized microcrystalline cellulose. A solvent-controlled chemoselectivity of the reaction was observed, leading to the chemodivergent synthesis of pyrrolines (2,5-dihydropyrroles) and pyrroles. The heterogeneous copper catalyst exhibits high efficiency and good recyclability in the Alder-ene reaction, constituting a highly attractive catalytic system from an economical and environmental point of view.

Artificial plant cell walls as multi-catalyst systems for enzymatic cooperative asymmetric catalysis in non-aqueous media.

The assembly of cellulose-based artificial plant cell wall (APCW) structures that contain different types of catalysts is a powerful strategy for the development of cascade reactions. Here we disclose an APCW catalytic system containing a lipase enzyme and nanopalladium particles that transform a racemic amine into the corresponding enantiomerically pure amide in high yield via a dynamic kinetic resolution.

Copper nanoparticles on controlled pore glass (CPG) as highly efficient heterogeneous catalysts for "click reactions".

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.

Sustainable Surface Engineering of Lignocellulose and Cellulose by Synergistic Combination of Metal-Free Catalysis and Polyelectrolyte Complexes.

A sustainable strategy for synergistic surface engineering of lignocellulose and cellulose fibers derived from wood by synergistic combination of metal-free catalysis and renewable polyelectrolyte (PE) complexes is disclosed. The strategy allows for improvement and introduction of important properties such as strength, water resistance, and fluorescence to the renewable fibers and cellulosic materials. For example, the "green" surface engineering significantly increases the strength properties (up to 100% in Z-strength) of chemi-thermomechanical pulp (CTMP) and bleached sulphite pulp (BSP)-derived sheets. Next, performing an organocatalytic silylation with a nontoxic organic acid makes the corresponding lignocellulose and cellulose sheets hydrophobic. A selective color modification of polysaccharides is developed by combining metal-free catalysis and thiol-ene click chemistry. Next, fluorescent PE complexes based on cationic starch (CS) and carboxymethylcellulose (CMC) are prepared and used for modification of CTMP or BSP in the presence of a metal-free catalyst. Laser-scanning confocal microscopy reveals that the PE-strength additive is evenly distributed on the CTMP and heterogeneously on the BSP. The fluorescent CS distribution on the CTMP follows the lignin distribution of the lignocellulosic fibers.