An intramolecular C-C formation process based on catalytic asymmetric oxetane opening by carbon nucleophiles has been developed, which provides rapid access to a range of valuable enantioenriched 2,3-dihydrobenzo[b]oxepines. With the combination of Sc(OTf)3 and a Box ligand, good chemical efficiency and enantioselectivity were achieved under mild conditions. The products are also useful precursors to other valuable structures, such as the bicyclo[3.2.2]nonane derivatives.