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Gnome's NetworkManager can't do what you want, but there is a little GUI tool that does it for you (no startup script needed)

nm-connection-editor (in case it's not installed: sudo dnf install nm-connection-editor)

First, you select your network interface. Then, under the General tab you can find a setting that says:

Automatically connect to VPN when using this connection

Check the box and you are good to go.