Personally I'd like for Ash to have Gallade and Weavile. Both Pokemon are very unlikely to be in his party, especially if you consider the fact that Weavile is Cyrus' strongest pokemon.
The only way I can see the weasel squirming into his party is if they gave him a pink one. It would be my favorite team member just for being pink. It could take itself very seriously, then throw a hissy fit whenever an opponent laughs it. Froslass is another possible snowpoint capture that would interest me, but I'd rather have Dawn get it so she can combat Zoey's Misdreavus.
Gallade is a pokemon I really like, but if its going to go to somebody its probably gonna be Nando.
Ash could get a Riolu, if the group comes across a mean trainer who owns one. The trainer doesn't have to be Paul, he's not the only mean trainer around. The Riolu's previous trainer ditches it when he/she become impatient with it. I'm just saying this on the basis that Riolu might be a rare enough Pokemon for most people to be ignorant about the happiness factor. The result of its past treatment makes it into a gloomy little fellow, coming out of its pokeball with a depressed frown and droopy aura antennas. In time it becomes happier, and eventually evolves into Lucario during an important battle. Something like that...
Spiritomb would be cool, but I can't think of a personality and/or scenario for its capture at the moment. Same thing for Gible.