After you talk to the "NPC" pokemon, the encounter starts with a real pok, which you can catch. And it looks like Synchronize works.
https://imgur.com/a/kUQJs
"Compound eyes" ability in PRO works only for accuracy. It does not increase the probability of items.
"Frisk" ability works good.
"Thief" move steals only if your pokemon does not hold items. Otherwise, it just kills the other pokemon.