This paper reviews chiral separations of primary amines by capillary electr
ophoresis and crown ether as chiral selector. Two possible mechanisms of ch
iral recognition by host-guest complexation are discussed: (i) The substitu
ents of the crown ether act as barriers for the guest compounds, and (ii) l
ateral electrostatic interactions between host and guest occur. Experimenta
l conditions affecting the separation are discussed in detail. A literature
overview of practical applications is presented as well. More than 80 diff
erent primary amines were analyzed, whereupon the majority could be resolve
d using a screening method. It is shown that a synergistic effect on the re
solution of chiral amines is observed when the chiral crown ether and cyclo
dextrins are simultaneously used in the same buffer system. This approach o
pens interesting perspectives for further method optimization.