Upcycling to Sustainably Reuse Plastics.

Plastics are now indispensable in daily lives. However, the pollution from plastics is also increasingly becoming a serious environmental issue. Recent years have seen more sustainable approaches and technologies, commonly known as upcycling, to transform plastics into value-added materials and chemical feedstocks. In this review, the latest research on upcycling is presented, with a greater focus on the use of renewable energy as well as the more selective methods to repurpose synthetic polymers. First, thermal upcycling approaches are briefly introduced, including the redeployment of plastics for construction uses, 3D printing precursors, and lightweight materials. Then, some of the latest novel strategies to deconstruct condensation polymers to monomers for repolymerization or introduce vulnerable linkers to make the plastics more degradable are discussed. Subsequently, the review will explore the breakthroughs in plastics upcycling by heterogeneous and homogeneous photocatalysis, as well as electrocatalysis, which transform plastics into more versatile fine chemicals and materials while simultaneously mitigating global climate change. In addition, some of the biotechnological advances in the discovery and engineering of microbes that can decompose plastics are also presented. Finally, the current challenges and outlook for future plastics upcycling are discussed to stimulate global cooperation in this field.

Visible Light-Driven Cascade Carbon-Carbon Bond Scission for Organic Transformations and Plastics Recycling.

Significant efforts are devoted to developing artificial photosynthetic systems to produce fuels and chemicals in order to cope with the exacerbating energy and environmental crises in the world now. Nonetheless, the large-scale reactions that are the focus of the artificial photosynthesis community, such as water splitting, are thus far not economically viable, owing to the existing, cheaper alternatives to the gaseous hydrogen and oxygen products. As a potential substitute for water oxidation, here, a unique, visible light-driven oxygenation of carbon-carbon bonds for the selective transformation of 32 unactivated alcohols, mediated by a vanadium photocatalyst under ambient, atmospheric conditions is presented. Furthermore, since the initial alcohol products remain as substrates, an unprecedented photodriven cascade carbon-carbon bond cleavage of macromolecules can be performed. Accordingly, hydroxyl-terminated polymers such as polyethylene glycol, its block co-polymer with polycaprolactone, and even the non-biodegradable polyethylene can be repurposed into fuels and chemical feedstocks, such as formic acid and methyl formate. Thus, a distinctive approach is presented to integrate the benefits of photoredox catalysis into environmental remediation and artificial photosynthesis.

Enantioselective Sulfoxidation Catalyzed by a Bisguanidinium Diphosphatobisperoxotungstate Ion Pair.

The first enantioselective tungstate-catalyzed oxidation reaction is presented. High enantioselectivities were achieved for a variety of drug-like phenyl and heterocyclic sulfides under mild conditions with H2 O2 , a cheap and environmentally friendly oxidant. Synthetic utility was demonstrated through the preparation of (S)-Lansoprazole, a commercial proton-pump inhibitor. The active ion-pair catalyst was identified to be bisguanidinium diphosphatobisperoxotungstate using Raman spectroscopy and computational studies.

Enantioselective Synthesis of Quaternary Carbon Stereocenters: Addition of 3-Substituted Oxindoles to Vinyl Sulfone Catalyzed by Pentanidiums.

A pentanidium-catalyzed highly enantioselective conjugate addition of 3-alkyloxindoles to phenyl vinyl sulfone has been demonstrated. This approach allows the construction of 3,3-dialkyl-substituted oxindole frameworks with high yield and excellent enantioselectivity (up to 99%) under simple phase-transfer conditions. A variety of oxindoles bearing all-carbon quaternary stereogenic centers were obtained in the presence of 0.25 mol% pentanidium. Meanwhile, practicality was illustrated by a gram-scale asymmetric synthesis of two 3,3-dialkyl-substituted oxindoles. The resulting adduct can be smoothly transformed to the natural product analogue in a short synthetic route.

Selective fluorination of alkyl C-H bonds via photocatalysis.

We report the generation of cationic N-radicals from Selectfluor® via energy transfer with anthraquinone as a photocatalyst for the fluorination of unactivated C-H bonds.