An efficient asymmetric intramolecular trapping of ammonium ylides of α-diazoketones with enones to synthesize indoline derivatives was realized. A Rh(II)/chiralN,N′-dioxide−Sc(III) complex bimetallic relay catalytic system was established. A series of optically active 2,2,3-trisubstituted indolines were obtained in high yields (up to 99%), good enantioselectivities (up to 99% ee), and excellent