A rhodium(III)-catalyzed indole C4-selective cyanation is described using the bench-stable, user-friendly electrophilic cyanation agent -cyano--phenyl--toluenesulfonamide (NCTS) as a coupling partner. A suitably positioned weakly coordinating -amide group was utilized for this site selectivity. The developed protocol proceeded with a broad scope. [Cp*Rh(MeCN)][SbF] was found to be an effective Rh(III) catalyst for this transformation. An initial study was carried out to know the photophysical properties of the C4-cyanated indole frameworks.
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