Hardly. Green Goblin and Doctor Octopus? Theres still plenty more. Venom was barely even shown in the last film so they could still make a whole movie out of him. I still don't understand why Venom and Carnage weren't made the villians in one of the previous films. Shocker, Mysterio, Kraven, etc. There's still plenty to work with. My knowledge of Spider-Man is limited to the 90s series so I could imagine there being two of those villians in one movie or something.
I could name a ton of spidey villains (Morlun, Hob-Goblin, Scorpion, Vulture, Rhino, etc.) but none of these guys seem iconic enough to carry the movie. Guys like Venom, Doc Ock, Sandman, and Green Goblin are the icons. They're the ones that caused Spidey the most grief. Throw in Carnage and people will think Cletus Cassidy is just Venom 1.5. Mysterio is pretty cool. Maybe Electro or Hydroman but they just don't seem like they'd translate well into a movie. I don't think Kraven the Hunter would, either. It's just like Batman. He has probably 100 enemies but the big guns are Joker, Riddler, Penguin, Two Face, Poison Ivy, and Catwoman. The rest (even my personal favorite, Bane) are either too obscure or too unbelievable. I'm actually shocked they made Ra's Al Ghul a movie villain and even more shocked that they made it work.