1.) When you have OpenVPN - why do you than use Teamviewer? Once connected over OpenVPN use Remote Desktop
2.) To be sure about Wake On Lan, you first need to test it locally on the network. Don't waste your time experimenting from remote, when it doesn't work locally.
3.) Google says, that pfSense can send WakeOnLan packets Opens a new windowto local computers. Test it while at home, so you will have it available when remotely.
4.) Connect via OpenVPN and test your favorite WoL app. Possibly it will work and you won't have to 'kick' your computer from the pfSense box. However don't expect it will work, when it did not work when you were normally connected to the local network.
5.) Leave Teamviewer just for cases, when OpenVPN doesn't work. It involves 3rd party networks and servers, so it's by definition less secure than a direct OpenVPN connection.