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Unable to connect to Exchange Server thru Cisco VPN

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Assuming you can ping the Exchange box and resolve the name while connected to the VPN, this could be an Authentication issue. Does the XP computer run Outlook 2007? Are you getting prompted for User/Pass everytime Outlook Opens or is it while you are trying to configure? (Do the credientials work, but it keeps asking for them OR do they not work at all?)

When setting up the Exchange account in Outlook, you enter the Server name and the User and click "Check Name" Try the "More Settings" and "Security" Tab. Select "Negotiate Authentication" (Default in 2007) Also Uncheck "Always prompt for logon credentials". NTLM Authentication is worth a try too.

Or try to type the full Domain\Username instead of just Username.

Or, ensure the User is not hidden from Exchange Lists in Active Directory.

Let us know how you make out. =]