87 octane gasoline is the equivalent of 87% iso-octane and 13% heptane. How the guys at the refinery actually achieve that number is
black magic. Because the refineries are mixing a whole lot of aromatics, the energy content can vary (and actually heptane has more energy than iso-octane)
Iso-octane is actually 2,2,4 - Trimethylpentane and has rating of 100 (Octane is where the Snow White and the 7 dwarves (carbons) are all in a row with a pail in each hand (hydrogen) with Snow White balancing one pail (hydrogen) on her ...s and Dopey having an extra pail (hydrogen) on stick up his... See Chemistry can be fun) 2,2,4 - Trimethylpentane is a messy combination.
Heptane has a rating of 0.
Having a rating better than 100 just means it is better than iso-octane. And a lot of compounds are better - ethanol (grain alcohol) is about 110, propane about the same, my favorite - triptane, or 2,2,3-trimethylbutane about 180.
Just because a rating is 0 (or less) doesn't mean it won't run in a spark ignition engine, just that it would a very low compression engine.
Back to the the black magic, when refineries were allow to use tetraethyl lead, they would refine gasoline to say 80 octane, then add TEL to raise rating to 87 as it was cheaper to add lead than to refine a better product. The stuff we pumped in 70's at my dad's garage had ~2 grams/gallon. That lead did a nice job of coating the valve seats, so manufacturers could run the valves directly on cast iron heads, so they were in no hurry for it to be replaced. It's that coating of valve seats that prevents it from being removed from Aviation fuel.
And we can thank catalytic converters for getting lead removed from gasoline.
I don't usually subscript to conspiracy theories, but we note Dupont's patent for R12 expired when the Ozone crisis was worst. Then right after we all to moved to R134a, all the noise about hole over Australia died off. And it should have been getting worse for next decade because the volume of historic R12 out there. Just saying.