Investigations on Gold‐Catalyzed Thioalkyne Activation Toward Facile Synthesis of Ketene Dithioacetals

Nucleophilic addition to thioalkynes was investigated under various catalytic conditions with gold(I) complexes being identified as the optimal catalysts. Structural evaluation of the product revealed an unexpected cis‐addition, arising from a gold‐associated thioketene intermediate. Based on this interesting mechanistic insight, a gold(I)‐catalyzed thioether addition to thioalkynes was developed as a novel approach to prepare ketene dithioacetals with good yields and high efficiency. The golden days: Nucleophilic addition to thioalkynes was investigated under various catalytic conditions with gold(I) complexes being identified as the optimal catalysts. Structural evaluation of the product revealed an unexpected cis‐addition, arising from a gold‐associated thioketene intermediate. Based on this interesting mechanistic insight, a gold(I)‐catalyzed thioether addition to thioalkynes was developed as a novel approach to prepare ketene dithioacetals with good yields and high efficiency.