Ive created a little code to keep a 3 day archive of specified directories, I am not sure why the Users directory wont copy. Most likely a security problem, when running the code as administrator there are no exceptions and no files are copied. If not elevated it will throw "UnauthorizedAccessException" which is expected.

Code:
Module ModuleSync
    Public Sub Main()
        Dim SourceFolders As New List(Of String)()
        With SourceFolders
            .Add("C:\Users")
        End With

        Dim Drive As String = "E:"
        If IO.Directory.Exists(Drive) Then
            Dim DestinationRoot As String = Drive & "\SYNCED"
            If Not IO.Directory.Exists(DestinationRoot) Then
                IO.Directory.CreateDirectory(DestinationRoot)
            End If
            Dim DestinationRemove As String = DestinationRoot & "\" & Date.Today.AddDays(-3).ToString("yyyy-MM-dd")
            DestinationRoot &= "\" & Date.Today.ToString("yyyy-MM-dd")

            If Not IO.Directory.Exists(DestinationRoot) Then
                IO.Directory.CreateDirectory(DestinationRoot)
            End If

            For Each Str As String In SourceFolders
                My.Computer.FileSystem.CopyDirectory(Str, DestinationRoot, True) 'Nothing is copied
            Next

            If IO.Directory.Exists(DestinationRemove) Then
                IO.Directory.Delete(DestinationRemove, True)
            End If
        End If
    End Sub
End Module