Formation of 2,4,4‐Trimethylthiete by Photodecarbonylation of 3,3,5‐Trimethyl‐2(3 H )‐thiophenone

A very attractive alternative to the hitherto sole entry (Hoffmann elimination of amines) to thiete derivatives such as 1 is provided by the title reaction. It is substantially milder—the thermally not very stable thietes can also be prepared at low temperatures—and enables a broad pattern of substitution. 1 reacts with water to give 4 ‐mercapto‐4‐methylpentan‐2‐one 2 .