A DFT Study on the Conversion of Aryl Iodides to Alkyl Iodides: Reductive Elimination of R−I from Alkylpalladium Iodide Complexes with Accessible β‐Hydrogens

Abstract DFT calculations have been performed on the palladium‐catalyzed carboiodination reaction. The reaction involves oxidative addition, alkyne insertion, C−N bond cleavage, and reductive elimination. For the alkylpalladium iodide intermediate, LiO t Bu stabilizes the intermediate in non‐polar solvents, thus promoting reductive elimination and preventing β‐hydride elimination. The C−N bond cleavage process was explored and the computations show that PPh 3 is not bound to the Pd center during this step. Experimentally, it was demonstrated that LiO t Bu is not necessary for the oxidative addition, alkyne insertion, or C−N bond cleavage steps, lending support to the conclusions from the DFT calculations. The turnover‐limiting steps were found to be C−N bond cleavage and reductive elimination, whereas oxidative addition, alkyne insertion, and formation of the indole ring provide the driving force for the reaction.