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The higher octane fuel is best utilized by the higher compression engines - it resists pre-detonation better, therefore reducing knock or ping, as stated earlier.
It's almost like the LOWER octane fuels are HOTTER fuels - they are more apt to "auto-ignite" in a high compression engine, like Matt said. Our engines are high compression, just not that high. I'm guessing anything higher than a 10:1 compression ration would dictate higher octane fuel.
Yeah!! Good rule of thumb. Let's call it the 8, 9, 10 rule  :
8:1 regular
9:1 mid
10:1 premium
Contra todo mal, mezcal; contra todo bien, también
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