Can you use alternation?
(?:\b|^)abc
UPDATE:
In Excel 2010 at least, \b
works as expected.
Sub test()
Set re = CreateObject("VBScript.RegExp")
re.Pattern = "\babc"
MsgBox re.test("abc")
re.Pattern = "^abc"
MsgBox re.test("abc")
re.Pattern = "(?:\b|^)abc"
MsgBox re.test("abc")
End Sub
The above outputs True, True, True for me.