as oxygen source, respectively. This open-flask method is safe and simple to operate, and no other chemical oxidants are required. Besides, inspired from the unique pathway of 1, 2-migration rearrangement, a highly controllable hydroxylation of indoles for the construction of C3a-hydroxyl iminium indolines was also developed. Mechanistic experiments suggest that a single-electron transfer-induced oxidation process is responsible for the tunable selectivity control.