Silver‐Catalyzed Stereoselective Aminosulfonylation of Alkynes

A silver‐catalyzed intermolecular aminosulfonylation of terminal alkynes with sodium sulfinates and TMSN3 is reported. This three‐component reaction proceeds through sequential hydroazidation of the terminal alkyne and addition of a sulfonyl radical to the resultant vinyl azide. The method enables the stereoselective synthesis of a wide range of β‐sulfonyl enamines without electron‐withdrawing groups on the nitrogen atom. These enamines are found to be suitable for a variety of further transformations. Controllable assembly: The first intermolecular aminosulfonylation of terminal alkynes with sodium sulfinates and TMSN3 is reported. This three‐component coupling, which shows excellent functional group tolerance, proceeds through sequential hydroazidation of the terminal alkyne and addition of a sulfonyl radical to the resultant vinyl azide. This enables the stereoselective synthesis of a wide range of β‐sulfonyl N‐unprotected enamines.