AbstractA facile and efficient method to produce optically pure benzofuroindolines, especially those without 3‐substituents that are susceptible to rearomatization, through [3+2] annulation of indoles with quinones is described. The suitable combination of a BOX ligand CuII hydrate complex and freshly activated molecular sieves functions to give controllably dynamic release of water, which enables the success of this reaction. This reaction can be performed on a gram scale with only 0.5 mol % catalyst loading.