Characterization and Application of Cyrene as a Biomass-Based Solvent for Homogeneous Heck-Coupling Reaction.

Cyrene, a renewable, non-toxic substance having negligible vapor pressure, even at high temperatures, was proposed as a reaction medium for homogeneous Pd-catalyzed Heck-coupling reactions. It was first characterized by its temperature-dependent physicochemical properties, i.e., vapor pressure, density, surface tension, heat capacity, and viscosity, the key parameters of its reaction and process chemistry. Its refractive indices in the function of temperature were also determined. Hereafter, the effect of reaction parameters (Pd source, nature of the base, the water content of the reaction mixture, leaving group (-I, -Br, -Cl, and -OTf of aromatic substrates) on Pd-catalyzed Heck-coupling reaction was investigated using iodobenzene and styrene as model substrates. Subsequently, 4-substituted iodobenzene and styrene derivatives were applied to investigate the effect of electronic parameters on the reaction efficiency and functional group tolerance. To demonstrate the applicability of the system, thirteen stilbene derivatives were isolated with good to high yields and purity (> 95%) using 0.2 mol% of Pd, 1.5 eq. of Et3N as a base, in 1 mL of Cyrene for 2 h at 100 °C.

Catalytic conversion of chitin-based biomass to nitrogen-containing chemicals.

The exploration of renewable alternatives to fossil fuels for chemical production is indispensable to achieve the ultimate goals of sustainable development. Chitin biomass is an abundant platform feedstock that naturally bears both nitrogen and carbon atoms to produce nitrogen-containing chemicals (including organonitrogen ones and inorganic ammonia). The expansion of biobased chemicals toward nitrogen-containing ones can elevate the economic competitiveness and benefit the biorefinery scheme. This review aims to provide an up-to-date summary on the overall advances of the chitin biorefinery for nitrogen-containing chemical production, with an emphasis on the design of the catalytic systems. Catalyst design, solvent selection, parametric effect, and reaction mechanisms have been scrutinized for different transformation strategies. Future prospectives on chitin biorefinery have also been outlined.

Palladium-Catalyzed Selective Amino- and Alkoxycarbonylation of Iodoarenes with Aliphatic Aminoalcohols as Heterobifunctional O,N-Nucleophiles.

Palladium-catalyzed amino- and alkoxycarbonylation reactions of aryl iodides were investigated in the presence of aliphatic heterobifunctional N,O-nucleophiles. Selective synthesis of amide alcohols and amide esters was realized, controlled by the base and substrate ratio. The effect of iodobenzene substituents was also studied with surprising results in terms of product selectivity. In addition to the model ethanolamine/iodobenzene system, various heteroaromatic substrates and numerous related nucleophiles were tested under optimized conditions, providing moderate to good yields of the target compounds. Reactions of serinol and 1,3-diamino-2-propanol as model trifunctional compounds showed particularly high chemoselectivity on amide ester products. Considering the coordinative properties of the applied nucleophiles, a rational catalytic cycle was proposed.

27 Years of Catalytic Carbonylative Coupling Reactions in Hungary (1994-2021).

Palladium-catalyzed carbonylation reactions, in the presence of nucleophiles, serve as very potent tools for the conversion of aryl and alkenyl halides or halide equivalents to carboxylic acid derivatives or to other carbonyl compounds. There are a vast number of applications for the synthesis of simple building blocks as well as for the functionalization of biologically important skeletons. This review covers the history of carbonylative coupling reactions in Hungary between the years 1994 and 2021.

Palladium-catalyzed Sonogashira coupling reactions in γ-valerolactone-based ionic liquids.

It was demonstrated that the γ-valerolactone-based ionic liquid, tetrabutylphosphonium 4-ethoxyvalerate as a partially bio-based solvent can be utilized as alternative reaction medium for copper- and auxiliary base-free Pd-catalyzed Sonogashira coupling reactions of aryl iodides and functionalized acetylenes under mild conditions. Twenty-two cross-coupling products were isolated with good to excellent yields (72-99%) and purity (>98%). These results represent an example which proves that biomass-derived safer solvents can be utilized efficiently in common, industrially important transformations exhibiting higher chemical and environmental efficiency.

Continuous flow hydrogenation of methyl and ethyl levulinate: an alternative route to γ-valerolactone production.

Heterogeneous continuous transformation of methyl levulinate (ML) and ethyl levulinate (EL) to γ-valerolactone (GVL), as a promising C5-platform molecule was studied at 100°C. It was proved that the H-Cube® continuous hydrogenation system equipped with 5% Ru/C CatCart® is suitable for the reduction of both levulinate esters. While excellent conversion rates (greater than 99.9%) of ML and EL could be achieved in water and corresponding alcohols, the selectivities of GVL were primarily affected by the solvent used. In water, 100% conversion and ca 50% selectivity that represent ca 0.45 molGVL gmetal -1 h-1 productivity towards GVL, were obtained under 100 bar of total system pressure. The application of alcohols as a solvent, which maintained high conversion rates up to 1 ml min-1 flow rate, resulted in lower productivities (less than 0.2 molGVL gmetal -1 h-1) of GVL. Therefore, from a synthesis point of view, the corresponding 4-hydroxyvalerate esters could be obtained even at a higher reaction rate. The addition of sulfonated triphenylphosphine ligand (TPPTS) allowed reduction of the system pressure and resulted in the higher selectivity towards GVL.

Catalytic Conversion of Carbohydrates to Initial Platform Chemicals: Chemistry and Sustainability.

The replacement of fossil resources that currently provide more than 90% of our energy needs and feedstocks of the chemical industry in combination with reduced emission of carbon dioxide is one of the most pressing challenges of mankind. Biomass as a globally available resource has been proposed as an alternative feedstock for production of basic building blocks, which could partially or even fully replace the currently utilized fossil-based ones in well-established chemical processes. The destruction of lignocellulosic feed followed by oxygen removal from its cellulose and hemicellulose content by catalytic processes results in the formation of initial platform chemicals (IPCs). However, their sustainable production strongly depends on the availability of resources, their efficient or even industrially viable conversion processes, and replenishment time of feedstocks. Herein, we overview recent advances and developments in catalytic transformations of the carbohydrate content of lignocellulosic biomass to IPCs (i.e., ethanol, 3-hydroxypropionic acid, isoprene, succinic and levulinic acids, furfural, and 5-hydroxymethylfurfural). The mechanistic aspects, development of new catalysts, different efficiency indicators (yield and selectivity), and conversion conditions of their production are presented and compared. The potential biochemical production routes utilizing recently engineered microorganisms are reviewed, as well. The sustainability metrics that could be applied to the chemical industry (individual set of sustainability indicators, composite indices methods, material and energy flow analysis-based metrics, and ethanol equivalents) are also overviewed as well as an outlook is provided to highlight challenges and opportunities associated with this huge research area.

Application of γ-Valerolactone as an Alternative Biomass-Based Medium for Aminocarbonylation Reactions.

γ-Valerolactone (GVL) was proposed as a renewable, nontoxic reaction medium with negligible vapor pressure for homogeneous Pd-catalyzed aminocarbonylation reactions. Iodobenzene as a model substrate and its 4-substituted derivatives were converted to the corresponding 2-ketocarboxamides with high conversions and chemoselectivities in γ-valerolactone. The effect of carbon monoxide pressure and reaction temperature on the conversion and selectivities were studied in the range 1-50 bar and 25-100 °C, respectively. The highest conversion and selectivity was achieved at 25 bar and 50 °C for iodobenzene in GVL for 24 h.

Fluorous hydrogenation.

The application of fluorous phosphine-modified catalysts for the hydrogenation of olefins is reviewed.

Fluorous hydroformylation.

The application of fluorous phosphine-modified catalysts for the hydroformylation of olefins is reviewed.