Thin air / the greek crash

I am not a pilot, and as much as my email address sounds like I am a
doctor, I'm not...

That said, I thought someone here might be able to help me out - they
news reports talk about passing out within seconds at high altitudes.
I understand the air is thinner / less O2.

But if I go underwater, there's certainly no air there. And I can stay
down for a while, holding my breath. How is high altitudes different?
I would think you would rasp / fight to breath in but keep functioning
as your body uses up the 02 in the blood from your last breath? Not
like a sleeping gas in the movies where you just keel over as soon as
it hits you?

THANKS!