Regiodivergent\nGold-Catalyzed Rearrangement–Addition\nReactions of Sulfenylated Propargylic Carboxylates with Indoles

Sulfenylated propargylic carboxylates were introduced\nto investigate\nthe influence of sulfur substitution in gold-catalyzed alkyne activation\npathways. Regiodivergent gold-catalyzed rearrangement and indole capture\nreactions proceed under mild conditions to give functionalized indole\nproducts bearing sulfenylated (<i>Z</i>)-enol carboxylate\nmotifs. Pathways involving both 1,2- and 1,3-carboxylate migrations\nare achieved selectively, with indole being added in a 1,4 relationship\nto the sulfenyl group in each case. High levels of selectivity are\ninfluenced by the catalyst system, counterion, and carboxylate group.