Its certainly possible...as for will it happen, the answer is almost certainly no.
Hotkey is a means to provide additional functions to the WPS/File-Browser, a need that arises from crowded keymaps and/or lack of physical buttons, not a means to duplicate functions that already exist based on personal preference.
Editing the keymap is fairly trivial (depending of course, on your individual definition of trivial).
There isn't just a file you can edit on the device that sets the functions of the keys, it needs to be edited in the source files before the binary is compiled. You will need to set up a development environment to compile Rockbox to achieve this.
The wiki has
many fine resources available to assist you in doing so.
The file you are looking for in particular is located in the Rockbox source at:
/rockbox/apps/keymaps/keymap-fuze.c
And (I'm writing this from memory, so...it may or may not be *absolutely* accurate) the part you'll want to edit is (or will look vaguely similar to

):
(ACTION_WPS_STOP, BUTTON_UP|BUTTON_REPEAT, BUTTON_UP ),
(it should be located around line 50 of keymap-fuze.c)which unless there are conflicts (which may well happen), you should be able to change to:
(ACTION_WPS_STOP, BUTTON_HOME|BUTTON_REPEAT, BUTTON_HOME ),
Hope this helps you achieve what you want to...
[St.]