Functionalized silica gels were applied as heterogeneous organocatalysts in PET glycolysis, and were recycled by filtration while preserving high monomer yields over five cycles.

The catalytic transformation of bio‐derived compounds, specifically 5‐hydroxymethylfurfural (HMF), into value‐added chemicals may provide sustainable alternatives to crude oil and natural gas‐based products. HMF can be obtained from fructose and successfully converted to 2,5‐diformylfuran (DFF) by an environmentally friendly organic electrosynthesis performed in an ElectraSyn reactor, using cost‐effective and sustainable graphite (anode) and stainless‐steel (cathode) electrodes in an undivided cell, eliminating the need for conventional precious metal electrodes. In this work, the electrocatalysis of HMF is performed by using green solvents such as acetonitrile, γ‐valerolactone, as well as PolarClean, which is used in electrocatalysis for the first time. The reaction parameters and the synergistic effects of the TEMPO catalyst and 2,6‐lutidine base are explored both experimentally and through computation modeling. The molecular design and synthesis of a size‐enlarged C₃‐symmetric tris‐TEMPO catalyst are also performed to facilitate a sustainable reaction work‐up through nanofiltration. The obtained performance is then compared with those obtained by heterogeneous TEMPO alternatives recovered by using an external magnetic field and microfiltration. Results show that this new method of electrocatalytic oxidation of HMF to DFF can be achieved with excellent selectivity, good yield, and excellent catalyst recovery.

This work presents the first successful applications of cinchona-thiosquaramides in asymmetric reactions. Binaphthyl-cinchona squaramides and thiosquaramides were synthesised, and then used as organocatalysts to promote the catalytic enantioselective Michael addition reaction of pentane-2,4-dione to trans-β-nitrostyrene with excellent yields (up to 99%) and enantioselectivities (up to 99% ee) at as low as 0.2 mol% catalyst loadings. Thiosquaramides gave higher enantioselectivities (up to 92% ee) in conjugate addition reaction of lawsone to β,γ-unsaturated α-keto ester than its oxo analogue, with high yields (up to 100%). Also, only thiosquaramide could catalyse the aza-Diels–Alder addition reaction of 2-siloxydiene to benzylideneacetone. Furthermore, quantum chemical computations showed that the geometrical structure of binaphthyl-cinchona thiosquaramide is similar to that of squaramide.