Except these sort of transfers almost always happen with, at a minimum, dual approval where exceptions cannot be made because it's software defining the rule.

1 employee submits the transaction for review, and a 2nd (and sometimes a 3rd, 4th) person must approve it before the payment initiates. There isn't typically a bypass function.

Also, CFOs are typically responsible for setting up and enforcing these controls. A big part of a CFO's job is to manage risk. If you work under a CFO, you would be more likely to be rewarded for following the process than be punished.

Obviously there are exceptions to this, but by and large no CFO would punish a finance person for disobeying an order to bypass a process intended to prevent financial fraud.