Yes, that can work, but when the button is pressed, you could get up to 260uA flowing through your MCU's input protection diode into the 3.3V rail. That could cause problems for the MCU. A Schottky clamp from the pin to the 3.3V rail would be advisable, which would also help satisfy the 0.4V max EN pin low threshold when the regulator output is disabled.
It gets more complex if you also want to be able to detect if the button is pressed while the MCU is running, and even more complex if you want to do that without using an extra I/O pin.