We report the design and synthesis of an indolyne that displays a reversal in regioselectivity, in both nucleophilic addition and cycloaddition reactions, compared to typical 4, 5-indolynes. Our approach utilizes simple computations to predict regioselectivity in reactions of unsymmetrical arynes. With this methodology, novel benzenoid-substituted indoles can be accessed with significant regiocontrol. Furthermore, the technology provides an ...