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There are very few opportunities to earn this achievement, but it can easily be farmed early on in your playthrough during the "The Home Fires Burn" mission.

As you works your way through the Haitian camp towards the chapel where Baka is located, make sure to pick up a firearm, preferably a handgun. After dealing with Baka, on your way out of the chapel, an enemy outside will start throwing molotovs at you. Take cover on the chapel's front "porch" and spot the molotov-throwing enemy.

He will always shout "throwing molotov," "firebomb," or "fire from the sky" just before he throws it. This is your indicator to shoot him quickly! If you time it perfectly, you will injure him, causing the enemy to drop the molotov and light himself on fire.

Once this happens, purposely get yourself killed and repeat this process until the achievement unlocks. It should take less then twenty minutes to get it done. Make sure you are not manually restarting the checkpoint; the enemies must kill you for progress to track properly.