β-chalcogen amines (β-CAs) are compounds containing an amino group and a chalcogen atom bonded to adjacent carbon atoms. The β-CA backbone is found in the proteinogenic amino acids cysteine and selenocysteine, and the synthetic analogues of this class exhibit diverse biological properties as well as useful applications in asymmetric catalysis. From a synthetic point of view, the preparation of the β-CA backbone poses significant challenges, especially when the goal is to obtain primary amines. In this sense, the decarboxylative ring-opening of 2-oxazolidinones by chalcogenolate anions appears as a convenient strategy. Although there are some reports on the synthesis of β-thioamines, there is a remarkable lack of studies in the preparation of primary and secondary β-seleno- and β-telluroamines. To address this gap, we focused our efforts on establishing a new methodology to allow a simple, rapid and modular synthesis of β-CAs from <i>non</i>-activated 2-oxazolidinone rings and diorganoyl dichalcogenides.After determining suitable reaction conditions, the method was extended to the synthesis of a library of primary and secondary β-CAs (Table 1). Remarkably, the developed one-step protocol enabled the preparation of β-selenoamines, β-telluroamines and β-thioamines with appreciable structural diversity and in yields of up to 95%. In general, we observed that the ring-opening reaction proceeded better with tellurium and selenium than with sulfur, which is consistent with the relative nucleophilicity of these species. Moreover, the steric hindrance caused by the neighboring R<sup>1</sup> group proved to be significant, given that L-valine and L-isoleucine derivatives were normally obtained in lower yields. In view of the potential applications of β-CAs and derivatives, we also carried out a scale-up study for this reaction from which we verified that the desired products are obtained in good yields at multigram scales.

Decarboxylative ring-opening of 2-oxazolidinones: A facile and modular synthesis of β-chalcogen amines

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