The training I am familiar with is to get as close as possible before taking such a shot with a pistol. It is such a scary situation, even if I am confident I would still fear hitting my wife in the hear just given human reaction times.
The closer you get to your target, the more you make yourself an easier target.
If you can get the bad guy to point the gun at you, you have a better chance of a debilitating shot without him shooting the hostage, making your hitting the "kill switch" less critical.
Otherwise, with his gun on the hostage, you have to hit the "kill switch" to prevent him from squeeing the trigger. That's in the occular-cranial area from the front. If you miss, a hit to the side of the skull can glance off bone, or a shot into the mouth will hit teeth and thick bone, blocking the shot from a quick kill.
The downside of getting him to not have his gun on the hostage is the gun is now in your direction. If you are very close, as you said, the chance of finding cover to protect yourself is much slimmer. If you're dead, you can't save anyone.
p.s. Call of Duty isn't "training".