Unfortunately there isn't a check valve on the passive (large) tank's fill port, so you would have to be quick with putting the cap back on after you unhooked the fill hose.
In theory though, it should be able to fill it if the nozzle has the right adapter. Most Class 8 on-road trucks have a gravity fill port for their DEF tanks so no anti-gravity burping for them.
2009 335d Sport - Space Grey
, Gloss Black
on Black Leather