Maybe someone else will share an easy way to get around the problem, but until then I'd suggest that you file a feature request in the Tracker. (check first to see if someone else has already reported this).
It shouldn't be sending another email if it's already sent one, I'd say, so that should probably be fixed (or maybe even already has been fixed).
What version of Moodle are you running?
Enrolment
Is It Possible to Get the Confirmation Link to Expire??
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