Reported herein is the first catalytic oxidative [4+2] cycloaddition of 2-aminophenols with cyclic enamines. This biomimetic catalytic oxidative strategy expediently accommodates the very labile structurally unbiased ortho-quinone monoimine intermediate for cycloaddition by controlling its formation rate, thus refraining from otherwise prerequisite steric or electronic stabilization and allowing efficient assembly of various tricyclic 1,4-benzoxazines in a step and atom economic fashion.