This sounds like a quiz question, and not presented by a student, but the professor testing the public on stackoverflow, but let's see...
Let's start with the One Definition Rule. It's clear neither version violates that, so they both pass that part.
Then, to syntax. Neither have syntax failures, they'll both compile without issue if you don't mind the potential blend of a syntax and semantic issue.
First, the simpler semantic issue. This isn't a syntax problem, but f(), in both versions, is the member of a struct, and the function clearly makes no change to the owning struct, it's returning a constant. Although the function is declared constexpr, it is not declared as const, which means if there were some reason to call this as a runtime function, it would generate an error if that attempt were made on a const S. That affects both versions.
Now, the potentially ambiguous return g(S()); Clearly the outer g is a function call, but S may not be so clear as it would be if written return g(S{}); With {} initializing S, there would be no ambiguity in the future should struct S be expanded with an operator() (the struct nearly resembles a functor already). The constructor invoked is automatically generated now, and there is no operator() to create confusion for the compiler at this version, but modern C++14 is supposed to offer clearer alternatives to avoid the "Most Vexing Parse", which g(S()) resembles.
So, I'd have to say that based on semantic rules, they both fail (not so badly though).