You can't use a WHERE clause with INSERT.
INSERT
always create a new record, it can't change existing ones.
Probably you want an UPDATE command instead:
UPDATE UserProfile SET Rented=@Rented WHERE [UserName]=@User
But, I wouldn't do it like that - I'd have a separate table for rented, which stored the DVD ID, the customer ID, the date of rental, and the date of return.
That way, the customer can borrow two DVDs for the weekend without your sytem having a fit, and you can "backtrack" to the previous renter if a customer comes in to say the disk is damaged and won't play, or is the wrong disk entirely.