Atom-economic and stereoselective catalytic synthesis of fully substituted enol esters/carbonates of amides in acyclic systems enabled by boron Lewis acid catalysis.

Carboacyloxylation of internal alkynes is emerging as a powerful and straightforward strategy for enol ester synthesis. However, the reported examples come with limitations, including the utilization of noble metal catalysts, the control of regio- and / selectivity, and an application in the synthesis of enol carbonates. Herein, a boron Lewis acid-catalyzed intermolecular carboacyloxylation of ynamides with esters to access fully substituted acyclic enol esters in high yield with generally high / selectivity (up to >96 : 4) is reported. Most importantly, readily available allylic carbonates are also compatible with this difunctionalization reaction, representing an atom-economic, catalytic and stereoselective protocol for the construction of acyclic β,β-disubstituted enol carbonates of amides for the first time. The application of the carboacyloxylation products to decarboxylative allylations provided a ready access to enantioenriched α-quaternary amides. Moreover, experimental studies and theoretical calculations were performed to illustrate the reaction mechanism and rationalize the stereochemistry.