The asymmetric aldol reaction of aldehydes with cycloalkanones using the catalyst 1a under environmentally friendly conditions gave the corresponding product in high yields with up to >99% ee. Unlike the organocatalysts reported thus far, the stereoselectivity of the products was controlled by using tilted 2,6-di fl uorophenylamide group of the catalyst 1a. As a result, the aldol reaction of aromatic aldehydes with cycloalkanones mainly proceeded by the attack of Si -face of the enamine on the Si -face of aromatic aldehyde due to the steric hindrance ( Fig. 1).