Hey, not a bad idea. I've never done that in this sort of case. Or rather, what I think is probably this sort of case. Because it's more likely it's just a bad design, and back to the drawing board.
But ... have you had an instance where your design was okay, then you got crap timing results. And then you thought, naaaah my code is awesome, the tools must be crap. Run smartxploder, and voila, you get some crap timing and some great timings. See! You knew it was those silly synthesis settings.
If yes, then: really? What kind of circuit was that, and what did ISE do to your design with default settings?
PS: All the cases where I've used smartxplorer was where I knew I was already asking for a little too much. But hey, engineer, so I want the last bit of performance that's to be had!