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If anything, pilots are more likely to be aware of the effects of hypoxia, there are training courses for it. If the cabin depressurises above 10,000 feet, there isn't enough oxygen to breathe. It still catches them off guard.
Nitrogen suffocation is also the method used for assisted suicide in the handful of places that allow it. So it's not like it's completely untested for these purposes. While I haven't read the results of research done for this, I'm sure it has been extensive.
I don't think it's some sort of silver bullet - there isn't one. The solution is rehabilitation, which is hard, but we shouldn't be killing people just because the right way is harder. However, if we're going to kill people, then nitrogen suffocation is more humane than any other method.