I mean, it's not like the optimization is impossible (by rejiggering the code a bit, it kicks in), it's just that using uint8_t's makes the optimzation far more brittle, because the compiler has to walk on eggshells around uint8_t's. Right?
In both cases, yes, if you hardcode the specific std::vector invariants in the compiler, it might be able to do better, but a user provided vector class wouldn't benefit from the same optimisations.
Note that compilers are not beyond hardcoding invariants of standard library facilities: malloc, C string functions, etc are treated as primitives by the compiler (for example, the result of malloc cannot alias with any other pointer), but for a complex class like vector, it does not seem appropriate and it is better to use compiler hooks in the implementation that are also available to the user (restrict, builtin functions, alias annotations, etc).
If the size and the buffer pointer are both private, wouldn't it be enough to analyze all the member functions to ensure that there is no aliasing between them? Users might try to muck around in the internal representation using memcpy or whatever, but that would presumably be undefined behavior.