The earliest you can this achievement is in chapter 6 you will learn how to throw money with Kiryu.
You'll come across a man and some thug or punks whatever they are asking for some money from a man. Once you beat them up talk to the man and he will show you how to throw money. The achievement will not unlock during the tutorial you'll need to complete the tutorial first.
Not sure if you can unlock by just randomly throwing money by hitting the
button with no thugs coming to attack you. I do know if they are coming attack you before they do attack you hit
button to throw the money and it should unlock.
But if you end up getting attack and have to fight them then you can not unlock the achievement you have to do it before they attack you.