Unique reactivity of a rhodium catalyst in the presence of many different Lewis basic additives was observed and studied. In the absence of additives, it was observed that a selective [2+2+2] reaction to form benzene products occurred; however, in the presence of an additive, optimally DMSO, the first rhodium(I)-catalyzed [2+2+2+2] reaction of alkynes occurred. A screen of different additives and catalysts was performed. Finally, a brief mechanistic study per-formed by using a ReactIR determined that DMSO coordinates to the catalyst, which affects the energetics of the reaction pathway. This appears primarily to raise the transition-state energy for the reductive elimination to form the benzene products.
