Bypassing the Inertness of Aziridine/CO Systems to Access 5-Aryl-2-Oxazolidinones: Catalyst-Free Synthesis Under Ambient Conditions.

The development of sustainable synthetic routes to access valuable oxazolidinones via CO fixation is an active research area, and the aziridine/carbon dioxide coupling has aroused a considerable interest. This reaction features a high activation barrier and thus requires a catalytic system, and may present some other critical issues. Here, the straightforward gram-scale synthesis of a series of 5-aryl-2-oxazolidinones was developed at ambient temperature and atmospheric CO pressure, in the absence of any catalyst/co-catalyst. The key to this innovative procedure consists in the direct transfer of the pre-formed amine/CO adduct (carbamate) to common aziridine precursors (dimethylsulfonium salts), replacing the classical sequential addition of amine (intermediate isolation of aziridine) and then CO . The reaction mechanism was investigated by NMR spectroscopy and DFT calculations applied to model cases.