var connectionString = ConfigurationManager.ConnectionStrings["Default"].ConnectionString;
connectionString.Expand() // returns "server=db01.mycompany.com;uid=uid;pwd=pwd;Initial Catalog=master;"
<configuration>
<appSettings>
<add key="Domain" value="mycompany.com"/>
<add key="ServerName" value="db01.{Domain}"/>
</appSettings>
<connectionStrings>
<add name="Default" connectionString="server={ServerName};uid=uid;pwd=pwd;Initial Catalog=master;" provider="System.Data.SqlClient" />
</connectionStrings>
</configuration>