A synthetic method that relies on Au(I)-catalyzed tandem 1,3-acyloxy migration/double cyclopropanation of 1-ene-4,9-diyne and 1-ene-4,10-diyne esters to construct the respective architecturally challenging tetracyclodecene and tetracycloundecene derivatives is described. Achieved under mild reaction conditions, the transformation was shown to be robust with a wide variety of substitution patterns tolerated to give the two members of the carbocyclic family in good to excellent yields and as a single regio- and diastereomer.

An efficient and expedient approach for the synthesis of unsymmetrical bis(3‐indolyl)methanes by employing a silica gel mediated Friedel–Crafts alkylation of 3‐indolylmethanols with various indoles is described. The synthetic utility of this transformation was demonstrated by reusing the silica gel up to 10 times without any apparent loss of reactivity.