Abstract: | A novel multicomponent cascade process is reported, based on the sequential combination between an initial nucleophilic attack step to an imine moiety and a palladium‐catalyzed oxidative heterocyclization‐alkoxycarbonylation process. By this new process, five simple molecules [2‐alkynylaniline imines, alcohol (ROH), carbon monoxide (CO), alcohol (ROH), and oxygen (O2)] are sequentially activated, selectively leading to high value‐added functionalized indole derivatives in a single operation. |