Hi,
The ideal point at which to separate challah today is once the dough has been formed, but before it has been divided into individual loaves.
In times when people were careful to keep their dough from becoming tamei [ritually contaminated], one would separate challah earlier in the process, right after the flour had become fully mixed with water, lest it become impure during the mixing and kneading process.
(Shulchan Aruch Yoreh Deah 327:2-3; Shach Yoreh Deah 327:6)
Have a great day,
Mordechai
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