Organic synthesis is usually performed in solution to dissolve both reactants and catalysts and to deliver heat. Here, we show that glycerol, which is a non-toxic, biodegradable, and recyclable liquid manufactured from renewable sources, has a high potential to serve as alternative green solvent for organic reactions. Several catalytic and non-catalytic reactions were successfully performed in glycerol. High products yields and selectivities were achieved. Besides solubility of the reactants and the catalysts and easy separation of the product, glycerol offers several other benefits such as catalyst recycling, microwave assisting reaction, and biphasic and emulsion modes.

Representative glycerol derivatives were employed as green solvents for selected organic transformations. In all reactions it was found that both reaction performance and product extraction yields were affected by solvent type and polarity. The solubility of the substrates in the solvent was the key step in product yield determination, while the product solubility in the reaction solvent determined the effectiveness of its extraction.

The investigation of the use of polysaccharides derived from natural sources to support metal catalysis has been the focus of several studies. Even though these molecules seem to be attractive materials, their full potential for use in support of heterogeneous catalysis still needs to be revealed. To that end, we developed a new preparation technique for polysaccharide-based palladium catalysts by immobilizing the palladium phosphine complexes on various renewable polysaccharides. The Suzuki cross-coupling in ethanol, using PdCl₂(TPPTS)₂ supported by various polysaccharides, was determined by gas chromatography and compared to homogeneous free-catalyst support. The PdCl₂(TPPTS)₂, that was immobilized on red algae supports, was successfully used as a heterogeneous catalyst in the Suzuki cross-coupling reaction, yielding high activity, higher than that of the homogeneous complex, without leaching. The FTIR spectrometry of representative heterogeneous polysaccharide-based TPPTS–PdCl₂ catalysts was compared to that of native polysaccharide and polysaccharide-based TPP–PdCl₂ catalysts, indicated on new bands, suggesting that the heterogenization occurs via interactions between the sulfonate group on the TPPTS and the hydroxyl groups on the polysaccharides. EDS and XPS analysis were also performed, confirming that the Pd complex was embedded within the i-carrageenan. A comparison of SEM images of i-carrageenan preparations also shed light on the interaction occurring between the polysaccharides and the TPPTS.

Aniline has been successfully produced by catalytic transfer hydrogenation of nitrobenzene in glycerol, which was employed as both a green solvent and a hydrogen donor. As a solvent, glycerol also facilitated easy separation of the product and recycling of the catalyst.

Polysaccharides derived from natural sources exhibit unique structures and functional groups, which have recently garnered them increased attention for their potential applicability as supports for metal catalysts. Renewable polysaccharide matrices were employed as supports for palladium complexes, with or without previous modification of the support, and were used in Suzuki cross-coupling of halobenzenes and phenylboronic acid derivatives. In this review, recent developments in the immobilization of palladium-based complexes are reported, including descriptions of the preparation procedures and catalytic activity of each system. In addition, the effects of the nature of the polymeric support and of the reaction conditions on catalytic performance are discussed.