The asymmetric aldol reaction of aldehydes with cycloalkanones using the catalyst 1aunder 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). The novel approach encouraged us to explore the reaction of other aldol donors and acceptors for a wide variety of application. In this work, unexpectedly, stereochemical preference was different from that in the reaction of aromatic aldehyde with cycloalkanone.Here we report the asymmetric aldol reactions of hydroxyacetones or aliphatic aldehydes with various aromatic aldehydes or isatins as aldol acceptors using our catalyst1.