A novel thermolytic distillation process was developed to depolymerize polyhydroxybutyrate (PHB) for the selective production of crotonic acid. The conditions adopted (170°C, 150 mbar) were applied to pure PHB and...

The valorization of alkenoic acids possibly deriving from biomass (fumaric and citraconic acids) was carried out through conversion in important building blocks, such as γ‐keto acids and succinic acid derivatives. The functionalization was carried out by addition onto the C=C double bond of radicals generated under photocatalyzed conditions from suitable hydrogen donors (mainly aldehydes) and by adopting a decatungstate salt as the photocatalyst. Syntheses were performed under batch (in a glass vessel) and flow (by using 3D‐printed reactors) conditions. The design of the latter reactors allowed for an improved yield and productivity.

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The hydroalkylation of nitroalkenes and β-nitroacrylates via a photocatalytic strategy has been optimised under both batch and continuous flow conditions. This target has been achieved by exploiting the potentialities of the decatungstate anion as a versatile hydrogen atom transfer (HAT) photocatalyst for the generation of alkyl radicals from aliphatic heterocycles, amides and cycloalkanes.

A library of unnatural α‐amino acid derivatives has been prepared via the hydrofunctionalization of the C=N bond in a set of compounds belonging to the family of α‐imino esters. The devised methodology capitalizes on the use of tetrabutylammonium decatungstate as the photocatalyst to generate C‐centered radicals from aliphatic and aromatic aldehydes, cyclic and acyclic oxygenated compounds and even cycloalkanes, via a hydrogen atom transfer (HAT) step. The best performance was observed when α‐hydrazono esters were employed in the role of radical traps, which delivered the corresponding (protected) α‐hydrazino acids as products. The versatility of the protocol was further demonstrated by the possibility to functionalize the herbicide safener isoxadifen‐ethyl.