For this trophy you'll need to complete Chapter 5: Plotting Behind the Scenes in Ultimate Adventure. Other than the free roaming and story-telling these are the battles you'll partake in during the chapter:
Guy vs Kisame
Konan vs Tobi (Madara)
Kyuubi Naruto vs Killer Bee
Tsuchikage (Akutsuchi & Kurotsuchi) vs Edo Deidara
Yamato (Kurotsuchi) vs Kabuto
Once the story progression and battle are finished you'll complete Chapter 5!