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

Gold‐catalyzed reactions of alkynyl N‐sulfinylimines were used to produce the corresponding 2H‐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. [ABSTRACT FROM AUTHOR]