A new type of Pd-catalyzed branching cyclizations of enediyne-imides towards furo[2,3-b]pyridines has been investigated with the help of DFT calculations. The role of the solvent DMF was probed based on the theoretical reaction mechanistic study. The chemical selectivity was investigated and found to be determined by the C[double bond, length as m-dash]C rotation step versus the (Cl-H + Pd-C(sp(2))) σ-bond metathesis step. In addition, the solvent effects were also elucidated to clarify why different solvents lead to different products.