A gold-catalyzed cycloisomerization of 1,6-diynes containing an ynamide propargyl ester or carbonate moiety has been developed that provides an attractive route to a diverse-substituted 3-acyloxy-1,4-dihydrocyclopenta[b]indoles. Mechanistic studies indicate that the reaction likely proceeds through a competitive 1,2-OAc migration followed by [3+2] cycloaddition of the vinyl gold-carbenoid intermediate with the pendant triple bond. The synthetic utility of the obtained cyclopenta[b]indole products was demonstrated by their efficient transformations by deprotection or double-bond isomerization reactions.
Liu J,Chen M,Zhang LW,et al. Gold(I)-Catalyzed 1,2-Acyloxy Migration/[3+2] Cycloaddition of 1,6-Diynes with an Ynamide Propargyl Ester Moiety: Highly Efficient Synthesis of Functionalized Cyclopenta[b]indoles[J]. Chem.-Eur. J.,2015,21(3):1009-1013.