Assuming a reasonably well supported USB chipset, I wouldn't expect it to be a problem. FreeBSD itself does not really differentiate between attachment technologies unless you dig down a bit. USB attached drives show up in a manner similar to SAS drives, but there's usually a bridge chip that is likely to make it so that certain things like SMART do not work. We discourage USB for pool storage because ... well, there's so many things wrong with that. However, for a boot device, especially if you get flash with a wear leveling controller, the main concern becomes what happens if the device becomes disconnected.