With the increasing restriction and control of hazardous solvents, safer alternatives need to be identified. Here a contemporary approach to solvent selection and substitution is presented that offers a more scientific alternative to the simple "like-for-like" exchange. A new family of levoglucosenonederived compounds is proposed, modeled to determine their solvent properties, synthesized, and tested. These new molecules show promise as replacements for polar aprotic solvents that have chronic toxicity issues, such as dichloromethane, nitrobenzene, and N-methylpyrrolidinone. The success of this approach makes it possible for academia and industry to make calculated, intelligent choices for solvent substitution in the future.

2-methyltetrahydrofuran (2-MeTHF) is a readily available, inexpensive, neoteric, bio-based solvent. It has been adopted across a wide range of chemical processes including the batch manufacture of fine chemicals, enzymatic polycondensations and ring opening polymerizations. To reduce the environmental burden related to the synthesis of pharmaceutical-grade polymers based on lactide and caprolactone, we envisaged the use of 2-MeTHF. For the first time, we combined a series of metal-free and enzymatic ROPs with free radical and controlled RAFT polymerizations (carried out separately and in tandem) in 2-MeTHF, in order to easily tune the chemistry and the architecture of the final polymers. After a simple purification, the amphiphilic polymers were formulated into nanoparticles and tested for their cytocompatibility in three model cell lines, to assess their application as potential polymeric excipients for nanomedicines. K E Y W O R D S2-MeTHF, green solvent, organo-enzymatic ROP, ROP-free radical tandem polymerizations, ROP-RAFT tandem polymerizations

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RAFT dispersion polymerisation of methyl methacrylate is performed in scCO2 with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight.