Through story progression this achievement can be earned.
From the start of Chapter 2: Their Reunion, besides special events, missions, requests, ect. these are the battles you'll partake in for the chapter.
Naruto vs Kiba
Naruto vs Sai
Naruto vs Yamato
Naruto vs Orochimaru (Boss Battle- S Rank)
Yamato vs Kyuubi Naruto
Naruto vs Sai
Sakura vs Kabuto
Naruto (Sakura & Sai as Support) vs Sasuke (Boss Battle- S Rank)
After your battle with Sasuke you'll complete Chapter 2: Their Reunion and earn 5G!