The VDD33USB pin supplies the USB internal transceiver. (On smaller packages its connected to VDD)
The VDD50USB pin is available on the larger packages as a 3.3V regulator input.
However, the regulator is disabled by default. The chip boots up in bypass mode (VDD33USB = power input), and you can enable the regulator to then supply that pin from VDD50USB.
That means that powering the STM32 won't work as the regulator won't get enabled.
I think the only selling point for having this regulator, is so you can power the MCU at VDD=1.8V and have USB operate in its own power domain of 3.3V. There are no specifications on this regulator, so its anyone's guess if it can deliver say 100mA for the STM32 part itself.
See 6.4.7 of the reference manual
(and perhaps AN5419)