It does not because the symbols to be exported are (supposed to be) only defined in Boost.ProgramOptions library. BOOST_SYMBOL_VISIBLE is always default visibility, no matter what.
Therefore anything in a Boost.ProgramOptions header would be made visible and thus exported, which equals exporting all the extern declarations. That, in turn, would cause ABI collision if somebody tries linking in a non-matching Boost, under the assumption that an internal Boost has been hidden from linkage (which "works", so far).
So how do you propose to setup a library such that exceptions can be caught by consumers of that library in a portable way? IMO the scenario you describe is impossible to support: Either everything is hidden, then exceptions can't be caught/dynamic_cast not used (according to docs on OSX) or it is VISIBLE, then you have potential collisions.