Thanks for the question @Andy!
For the card's ability we have: React, Boot: When this dude is aced or discarded in a shootout, send one dude in this shootout home booted and draw a card.
The timing of this occurs right when the dude would be Aced or Discarded. You can choose any dude in the shootout as an eligible target for the effect, even the dude that's carrying the goods. However, the ability is not a replacement effect (it doesn't say 'instead'). So while your dude would go home booted, the dude would still be Aced or Discarded. You would get a card draw out of it though.