
Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Янв. 1, 2025
Herein, we report an HFIP-mediated, versatile, sustainable, atom-economical, and regio- stereoselective hydro-functionalization of ynamides with various S-nucleophiles (1 equiv.) such as thiols, thiocarboxylic acids, carbamates, xanthates, O,O-diethyl S-hydrogen phosphorothioate to access a wide variety stereodefined trisubstituted ketene N,S-acetals under mild conditions. This protocol requires only HFIP, which plays multiple roles, acting Brønsted acid protonate the ynamide regioselectively at beta carbon generate reactive keteniminium intermediate, stabilizing intermediate solvent through H-bonding. After nucleophilic attack S-nucleophile on deprotonation, HFIP is regenerated in most cases can be easily recovered recycled, revealing high sustainability protocol. Remarkably, all reactions are highly efficient furnish excellent yields many pure products were obtained just by washing crude reaction mixture pentane. Significantly, green chemistry metrics found excellent.
Язык: Английский