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Why not have them be Loot Allies with a special trait you come up with. Then create a barrier that, if defeated, allowed you to choose one Loot Ally with that special trait from the box and add it to your hand. That takes care of how you get them.
I'm not sure of the math, but it seems like a single barrier might be just as rare as a single ally, given that there are usually fewer barriers in a given scenario.
What you said did just give me yet another idea, though. It would be very interesting to have a set of solo scenarios, each unique to a character, that plays out as either a flashback or some other interlude and has the respective companion/favored boon as the scenario reward. These could offer a lot of extra flavor to each character. The only problem is that I'm not very well versed in the Pathfinder mythos. Any help would be appreciated :)