Kind of hard to narrow it to 5. Are you wanting pointer controls? Waggle controls? A few that come to mind as having memorable controls include:
Red Steel 2 Excitebots Skate It Goldeneye Metroid Prime Trilogy Mario Galaxy 1 & 2 [although I prefer the second game] Skyward Sword Wii Sports Resort NBA Jam --- Now Playing:Body Harvest, Donkey Kong 64, Jet Force Gemini, Syphon Filter
In order: RE4 Wii Edition Conduit 2 Red Steel 2 The Conduit Metroid Prime 3/Trilogy --- "Saying Metroid Other M is better than the Prime Trilogy because you hate shooters is like saying Aliens:CM is better than FF7 because you hate RPGs.
And Mario Galaxy 2 is one of the best in terms of the feel of jumps, registering when you want to grab on to a cliff, moving mid-jump.... Plus the fairly interesting 'balence on top of a ball' Wii Remote modes. Oh yeah, also the fairly cool Yoshi IR pointing mode.