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New sustainable concepts have to be developed to overcome the increasing problems of resource availability. Cellulose derivatives with tunable material properties are promising biobased alternatives to existing petroleum-derived polymeric materials. However, the chemical modification of cellulose is very challenging, often requiring harsh conditions and complex solubilization or activation steps. More sustainable procedures toward novel cellulose derivatives are therefore of great interest. Herein, we describe a novel concept combining two approaches, (i) tandem catalysis and (ii) cellulose derivatization, by applying a single catalyst for three transformations in the DMSO/DBU/CO 2 switchable solvent system. Cellulose was functionalized with four different biobased isothiocyanates, which were formed in situ via a catalytic sulfurization of isocyanides with elemental sulfur, preventing the exposure and handling of the isothiocyanates. The degree of substitution of the formed O- cellulose thiocarbamates was shown to be controllable in a range of 0.52-2.16 by varying the equivalents of the reactants. All obtained products were analyzed by ATR-IR, 1 H, 13 C, and 31 P NMR spectroscopy as well as size exclusion chromatography, elemental analysis, differential scanning calorimetry, and thermal gravimetric analysis. Finally, the tandem reaction approach was shown to be beneficial in terms of efficiency as well as sustainability compared to a stepwise synthesis. Recycling ratios ranging from 79.1% to 95.6% were obtained for the employed components, resulting in an E -factor of 2.95 for the overall process.

Marine plastic pollution is a worldwide challenge making advances in the field of biodegradable polymer materials necessary. Polylactide (PLA) is a promising biodegradable polymer used in various applications; however, it has a very slow seawater degradability. Herein, we present the first library of PLA derivatives with incorporated "breaking points" to vary the speed of degradation in artificial seawater from years to weeks. Inspired by the fast hydrolysis of ribonucleic acid (RNA) by intramolecular transesterification, we installed phosphoester breaking points with similar hydroxyethoxy side groups into the PLA backbone to accelerate chain scission. Sequence-controlled anionic ring-opening copolymerization of lactide and a cyclic phosphate allowed PLA to be prepared with controlled distances of the breaking points along the backbone. This general concept could be translated to other slowly degrading polymers and thereby be able to prevent additional marine pollution in the future.