One-pot combinations of sequential catalytic reactions can offer practical and ecological advantages over classical multi-step synthesis schemes. In this context, the integration of enzymatic and chemo-catalytic transformations holds particular potential for efficient and selective reaction sequences that would not be possible using either method alone. Here, we report the one-pot combination of alcohol dehydrogenase-catalysed asymmetric reduction of 2-azido ketones and Pd nanoparticle-catalysed hydrogenation of the resulting azido alcohols, which gives access to both enantiomers of aromatic 1,2-amino alcohols in high yields and excellent optical purity (ee >99%). Furthermore, we demonstrate the incorporation of an upstream azidolysis and a downstream acylation step into the one-pot system, thus establishing a highly integrated synthesis of the antiviral natural product (S)-tembamide in 73% yield (ee >99%) over 4 steps. Avoiding the purification and isolation of intermediates in this synthetic sequence leads to an unprecedentedly low ecological footprint, as quantified by the E-factor and solvent demand.
Nowadays, the chemical industry is looking for sustainable chemicals to synthesize nanocomposite bio-based polyurethane foams, PUs, with the aim to replace the conventional petrochemical precursors. Some possibilities to increase the environmental sustainability in the synthesis of nanocomposite PUs include the use of chemicals and additives derived from renewable sources (such as vegetable oils or biomass wastes), which comprise increasingly wider base raw materials. Generally, sustainable PUs exhibit chemico-physical, mechanical and functional properties, which are not comparable with those of PUs produced from petrochemical precursors. In order to enhance the performances, as well as the bio-based aspect, the addition in the polyurethane formulation of renewable or natural fillers can be considered. Among these, walnut shells and cellulose are very popular wood-based waste, and due to their chemical composition, carbohydrate, protein and/or fatty acid, can be used as reactive fillers in the synthesis of Pus. Diatomite, as a natural inorganic nanoporous filler, can also be evaluated to improve mechanical and thermal insulation properties of rigid PUs. In this respect, sustainable nanocomposite rigid PU foams are synthesized by using a cardanol-based Mannich polyol, MDI (Methylene diphenyl isocyanate) as an isocyanate source, catalysts and surfactant to regulate the polymerization and blowing reactions, H2O as a sustainable blowing agent and a suitable amount (5 wt%) of ultramilled walnut shell, cellulose and diatomite as filler. The effect of these fillers on the chemico-physical, morphological, mechanical and functional performances on PU foams has been analyzed.
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