Understanding and ModulatingIndolyne Regioselectivities

Heterocyclic arynes hold much promise for applications in modern synthetic chemistry. One particular class of hetarynes is those derived from the indole heterocycle (i.e., indolynes). In- dolynes can be generated under mild fluoride-based reaction condi- tions using silyltriflate precursors. Indolyne-trapping experiments provide access to benzenoid-substituted indoles in a controlled manner with synthetically useful yields. Regioselectivities can be predicted prior to experiments using simple calculations, ultimately allowing for the modulation of selectivities by careful design. This strategy has enabled a concise synthesis of indolactam V.