Well there are some things to consider. Initially if you could make sure that after you blow up an asteroid you will end up with numerous but small enough pieces so that they will either: one, burn up in the atmosphere or two, be headed away from Earth (and not hitting us five years later) then we are OK, and blowing up the asteroid with a missile would be a fair solution.
The problem here lies in the fact that we know little about the internal composition of asteroids in general, and presumably even less about a particular one, so it is very hard to predict exactly where the pieces of the asteroid generated by an impact are or aren't going to end up or, be headed towards or even its size.
Another scenario could be that if you effectively smashed the asteroid into small pieces that could then burn into the atmosphere, and if those pieces were coincidentally to end up being consumed by Earth's atmosphere, it would heat up provoking presumably an unpleasant day on Earth of course depending on the mass of the object.
But there is a much better solution than that Armageddon-Hollywood inspired one. It is call gravitational tethering. There is something we know, and we know very well about asteroids, and that would be their trajectory paths or orbits. Even when a new asteroid is discovered, its orbit can be computed pretty quick and with great accuracy (because we know the solar system's gravity very well). So if an asteroid is to impact Earth, it is likely that we will know with years, probably decades in advance. And so we can just send a space vehicle (called gravity tractor), with enough mass and time in advance, and place it just beside the asteroid, hence allowing us to tilt its orbit by just a tiny amount, due to the gravitational pull between the two objects. Now when you consider the effect of that tiny amount in the long run, it effectively deflects the path of the given asteroid from that of the Earth so that it won't hit us 20 or 30 years later.
And this is something we have control over, and something we can predict with great accuracy. It is the (safe) way to go.
If you are still not happy with my answer, you can listen to Neil de Grasse Tyson himself explaining it in this 5 min video.
Also check out this talk from the American Museum of Natural History on "Defending Earth from Asteroids" LINK
Further reference here.