Jigglypuff and Toon Link both require special unlocking conditions in SSE (beat game, go to hidden location in level, challenge, beat, rinse, repeat), so the Classic mode might be the better option (though if it won't work for you, it's no help at all)... you could always go with the Vs. Mode unlocks, though, and I know for a fact Wolf is hardest to unlock at 450, so it probably won't take long if you just keep playing.
EDIT: according to Wikipedia;
JIGGLYPUFF- 350 Vs. matches, or beat Event 20
TOON LINK- 400 Vs. matches, or beat Classic with Link after beating the Subspace Emissary
Not sure if this is true (Event 20 looks a bit iffy) but it'd be worth a look, imo.