It does nothing as if the PC was offline? (like it doesnt see the folder) Sounds to me like there are connection issues with the vpn client.
1.If the client logs in and then opens the VPN tunnel, Windows authenticated the password locally and not with the domain controller. The gateway, DNS and WINS were therefore initially provided by the ISP up until the tunnel was opened. If the VPN software could be run prior to logon, windows will authenticate with a domain controller (you have a Domain I take it) and things become far more reliable... It will authenticate correctly, apply mapped shares, group policies, login scripts will run and the TCP stack will be allocated in the correct fashion. Most VPN software allows this option of logging in after running the vpn software - its worth checking this out as selecting this option makes the tunnel much more reliable. What Chris is suggesting would be a viable workaround in theory, it just depends if the tunnel remains up after logoff - some do, some dont.
2.Usually, VPN software uses a virtual IP address using a virtual adapter. Once the tunnel is opened this virtual IP address will be assigned the correct corporate tcp settings. If the binding order for the virtual address is lower than the real adapter, the real adapter has a habit of taking priority so mapping shares often fails as the PC is looking at the wrong gateway.
If you go to Network connections, Advanced, Advanced Settings, Look at the connections and there should be a list of adapters. Select the local area connection that corresponds to the VPN client and use the arrows on the right to make the binding order higher than the real network adapter. This will help ensure that when the VPN software is run, windows should use the correct tcp settings and be able to see the network correctly as the virtual adapter will take priority.
3. Does the VPN software allow split tunnelling? If it does and the user doesnt need to access local resources like shares or printers locally then turn this option off as once again it makes things more robust. It also helps clear things up if the VPN concentrator uses a similar IP range to the address the client is actually on.
4. What transport method does the VPN client use? IPSEC over TCP or UDP? Some dsl routers dont like UDP... TCP is slower but a more reliable option should you have the control.
All or any of the above may help with your issues. Its worth working through them to see if they improve matters.