Second/rear curtain sync is widely misunderstood. It can be brilliant but it's no magic bullet and there are good reasons why first-curtain sync is the default.
For example, second-curtain sync doesn't work at all until shutter speeds drop below 1/30sec, and even then the flash fires well before the end of the exposure - it's more like middle-sync. Only at significantly longer speeds does the flash get relatively closer to the end of the exposure. Pocket Wizard's Mini/Flex system can tighten this up usefully, but the OEM defaults are sloppy.
There is a widely held belief that by firing the flash last it somehow overlays the flash image more prominently. This is untrue - if you want a clearer flash image, then it must fall over a dark area of the background.
There are other problems. With longer shutter speeds, second-curtain sync makes timing the moment much more difficult, and fleeting gestures and expressions are hard to capture. When used with auto-TTL enabled, the pre-flash makes subjects think that the picture has been taken, and they move. And when the pre-flash and main flash are quite close together, there's a good chance you'll capture the subject blinking.
On the other hand, second-curtain sync works really well if your subject is a) moving, and there is some usable ambient light, b) it's moving in a predictable direction, and c) the direction of that movement is important. In that situation, second-curtain sync will put the ambient blur behind the subject, and the subject will be less obscured by that ambient blurring. Well illustrated in comparison graphics here
http://neilvn.com/tangents/first-curtain-sync-vs-rear-curtain-sync/