Formation of β‑Oxo‑N‑vinylimidates via Intermolecular Ester Incorporation in Huisgen Cyclization/Carbene Cascade Reactions

Unusual intermolecular trapping of esters by carbenes generated via a Huisgen cyclization/retro­electro­cyclization/dediazo­tization cascade reaction is presented. β-Oxo-N-vinyl­imidates could be obtained in one step from propargyl carbonazidates. Mechanistic control experiments suggested reversible dipole formation by ester addition to the carbene, and nitrogen attack to the ester carbonyl was irreversibly followed by stereoselective decarboxylative elimination to give the Z-vinyl imidate. The cross-conjugated enone, imidate, and enamine functional groups in the β-oxo-N-vinylimidates offer novel syntheses of functionalized oxazoles.