Consecutive O−S/N−S Bond Cleavage in Gold‐Catalyzed Rearrangement Reactions of Alkynyl N‐Sulfinylimines

Abstract Gold‐catalyzed reactions of alkynyl N ‐sulfinylimines were used to produce the corresponding 2 H ‐azirines possessing sulfenyl and acyl groups at the 3‐position of the azirine ring in good to excellent yields. These reactions involved internal transfer of the sulfinyl oxygen atom to form a thiooxime intermediate tethered to an α‐oxo gold carbene moiety. Subsequent insertion of the carbene into the N−S bond resulted in ring construction.