Generally used and highly reactive RMgBr reagents were effectively deactivated by bis[2-(N,N-dimethylamino)ethyl] ether and then were employed in the highly enantioselective addition of Grignard reagents to aldehydes. The reaction was catalyzed by the complex of commercially available (S)-BINOL and Ti(O'Pr-)(4) under mild conditions. Compared with the other observed Grignard reagents, alkyl Grignard reagents showed higher enantioselectivity and they achieved >99% ee.