A direct route to chiral beta-fluoroamines with tetrasubstituted C-F centers through the organocatalytic Mannich reaction of alpha-fluoro cyclic ketones and alpha-amidosulfones by using a chiral oligoethylene glycol as a cationbinding catalyst and KF as a base is reported. For most substrates, nearly perfect enantioselectivities were achieved even at very high temperatures (> 80 degrees C). The salient features of this process include a) a transition-metal-free and operationally simple procedure, b) direct use of aamidosulfones as bench-stable precursors of sensitive imines, c) direct enolization of racemic a-fluoro cyclic ketones, and d) excellent stereoselectivity up to 99% enantiomeric excess and > 20: 1 diastereoselectivity (anti/syn). Thus, this protocol is easily scalable and provides a new approach for the synthesis of biologically relevant products with tetrasubstituted C-F centers. Furthermore, this protocol was also successfully extended to generate C-Cl and C-Br quaternary stereogenic centers.