The proposal itself explains why: to allow overloading with the underlying types of uint_least16_t and uint_least32_t. If they were typedefed this wouldn't be possible.
Define char16_t to be a distinct new type, that has the same size and representation as uint_least16_t. Likewise, define char32_t to be a distinct new type, that has the same size and representation as uint_least32_t.
[N1040 defined char16_t and char32_t as typedefs to uint_least16_t and uint_least32_t, which make overloading on these characters impossible.]
As for why they aren't in the std namespace, this is for compatibility with the original C proposal. C++ prohibits the C definitions from appearing in its own version of <cuchar>
[c.strings] / 3
The headers shall not define the types char16_t, char32_t, and wchar_t (2.11).
The types then would need to be global typedefs, which carries its own set of issues such as
typedef decltype(u'q') char16_t;
namespace foo {
typedef int char16_t;
}
The reason for std::nullptr_t not being a keyword can be found in the question you linked
We do not expect to see much direct use of nullptr_t in real programs.
making nullptr_t the real exception here.