Avengers Party: Capture the Villian! This was a huge hit with the kids and parents. Buy a lot of streamer because the kids just want to keep wrapping their parents! Just beware, there's a lot of clean up afterwards.
This continues during his time as Winter Soldier, when random people are rescued from alleys. His handlers have no idea wtf is going on when he darts off into alleys, but assume he's found a less obvious route to attack from.