AbstractThe gold‐catalyzed annulation of alkynylsulfones, involving pyridine N‐oxides (as O‐atom transfer reagents) and nitriles (as C=N synthons), comprises a diazo‐free route to valuable 4‐sulfonyl‐1,3‐oxazoles. This reaction operates under relatively mild conditions (IPrAuNTf₂ 5 mol %, rt or 60 °C), and a number of functionalities was compatible (35 examples; 14–95%). In most cases, the SO₂ fragment, which is typically expulsed in the previously reported Au‐catalyzed O‐transfers to alkynylsulfones, retains in the heterocyclic products. The postulated reaction mechanism suggests a key role of reactive gold α‐oxo carbene intermediates formed via the O‐atom transfer.magnified image