A sustainable MAO-N biocatalyzed process for the synthesis of pyridines from aliphatic tetrahydropyridines (THP) has been developed. Pyridine compounds were synthesized under mild reaction conditions and with high conversion exploiting MAO-N whole cells as aromatizing biocatalysts. The kinetic profile of the whole cell biocatalytic transformation was finally investigated via in situ 19 F NMR.
The unprecedented Trametes versicolor laccase/TEMPO-catalyzed aromatization of 2,5-dihydrofurans to furans is described. A variety of furan derivatives have been synthesized in moderate to high conversions (21−99%) and yields (20−76%) under mild reaction conditions. This work reveals the aromatization ability of the Trametes versicolor laccase/TEMPO system in synthesizing oxygen-containing heterocycles. Moreover, the direct synthesis of furans from aliphatic diallyl ethers through a chemo-enzymatic metathesis/ aromatization cascade, which combines Grubbs-catalyzed ring-closing metathesis and laccase/TEMPO-catalyzed aromatization in the same reaction medium, has been successfully developed.
Secondary amines are obtained with low environmental impact with a minimal amount of surfactants and organic solvents (biomass derived) employed only for product separation.
Herein, we report the use of γ-valerolactone as a new biomass-derived reaction medium for microwave assisted organic synthesis. The interaction of this solvent with microwaves and its heating profile under microwave irradiation has been fully characterized for the first time, demonstrating its stability and the applicability in microwave assisted Pd/C catalysed reactions avoiding the arcing phenomena frequently observed in these conditions. The use of γ-valerolactone demonstrated to be compatible with aliphatic and aromatic amines in the hydrogen transfer Pd/C mediated synthesis of benzimidazoles.
In the presence of Shvo's catalyst [2,3,4,5‐tetraphenyl‐1,3‐cyclopentadien‐1‐ol, ruthenium(II) complex], a small quantity of aniline and TGPS‐750‐M surfactant, terminal alkynes were hydrated under microwave (MW) dielectric heating in water as solvent with high conversion and good yield. The reaction gives the Markovnikov product exclusively, unlike that commonly observed with ruthenium complexes. Under the influence of MWs, Ru nanoparticles embedded in the nanomicelle environment were formed, acting as the effective hydration catalyst. Introducing sodium formate in the aqueous phase and using a stoichiometric amount of amines, the Ru nanoparticle nanomicelle catalyst gave the first example of one‐pot single‐step hydroamination of alkynes with the formation of the corresponding secondary amines. The reaction is characterized by low environmental impact as TGPS‐750‐M is required in low amount, and organic solvents employed only for product separation or catalyst recycling.
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