What happened to the wall?
Water has penetrated the structure of the wall and is emerging behind the paint, forcing it off. There may also be efflorescence, depending on the material the wall is constructed from.
Is it a re-pointing issue?
Probably not.
The surface of the wall is uneven overall, this might be a sign that this problem has occurred before.
If the problem recurs after fixing all the other possible causes, I would then consider re-pointing the exterior of the wall (presumably a brick wall) and/or applying a water repellent intended for that purpose & material.
I accidentally [left] the window open and by the time I [found] it, there [was] some rain on the [window's] wood frame.
This is probably the cause. Water penetrated past the window sill. You may be able to make the area more water resistant but the best way to prevent a recurrence is to keep the window shut when it is raining.
We just replaced the roof [a] couple [of] days ago
Then that could also be a suspect, I'd check the wall structure above the window for high humidity (you can get humidity testers for walls). If the underside of the new roof is accessible, I'd also inspect that for signs of water penetration.
there's a missing medal(sic) that the roofer hasn't installed yet
Depending what this is (flashing?, guttering?), it's absence could have contributed to the problem.