Marvel, not just MCU. If it's Marvel, it counts.
For theatrical release, I think it's Punisher: War Zone
There is a Captain America movie from the early 90s that went straight to video, so it's probably that one, or at least one like it that precedes the modern "MCU".
Fantastic four. The one with Michael b Jordan.
I'm guessing iron man 2
Probably Ghost Rider 2 or the new Fantastic Four ...