It's a solution, but I don't see any merit in resorting to this. As was previously said, fat free, is not a replacement for writing regular php. If you want to define constants, the easiest is to either put a block of them at the top of your index.php or put them in a file named something like constants.php and just list the define statements one after another.
Constants are typically things set by developers, whereas config files are meant to be edited by the installer or user (of your software). Typically, you do not wish to expose constants to being changed by anyone except a developer.
The entire purpose and efficiency of config files, is that you do not have to process them manually. You call $f3->config() to do that and everything is imported into the HIVE. Now you want to put some overhead on top of that. Remember, this overhead will have to execute for every page you load. The fat free concept is to be as lean as possible. Iterating over a HIVE array to create constants adds fat.