At the end of the game (bearing off), which of the following moves are valid?
No, the second one is not valid.
There are many different rule sets for Backgammon. However, I'm unaware of any which would allow it.
This quote is from Wikipedia. It is footnoted as coming from both Backgammon for Winners, and Hoyle's Rules of Games.
A die may not be used to bear off checkers from a lower-numbered point unless there are no checkers on any higher points.