ORDER BY actually happens last.

    jamie=# (select a, a+1 as c from nums) order by b,c;
     a | c 
    ---+---
     3 | 4
     0 | 1
     1 | 2
     2 | 3

(4 rows)

It's a separate part of the grammar:

    <query primary> ::=
        <simple table>
      | <left paren> <query expression body> [ <order by clause> ] [ <result offset clause> ] [ <fetch first clause> ] <right paren>

But, if "QE is a <query expression body> that is a <query term> that is a <query primary> that is a <simpletable> that is a <query specification>" then the <order by clause> may select columns from the <table expression> even though those don't really exist any more by the time the <order by clause> runs. It's tricky to implement.