Copper‐ and Palladium‐Cocatalyzed Intramolecular C–H Functionalization/C–N Bond Formation: A Route to the Synthesis of Indoloisoquinoline Derivatives

A Cu and Pd bi‐catalytic system is found to be very effective for the indole C2–H functionalization/C–N bond formation process.This is a unique reaction in which isoquinoline systems were synthesized from aldoximes rather than from ketoximes. During the reaction Cu(OTf) 2 converts the aldoximes into the corresponding cyanides and indoloisoquinolines, but introduction of Pd(OAc) 2 changes the outcome of the reaction significantly, by suppressing the formation of cyano products, thus giving exclusively indoloisoquinolines. A range of substituted indoloisoquinolines and aza‐indoloisoquinolines are prepared in good to very good yields under air.