I don't think it's possible with Hibernate. Have a look here :
http://www.hibernate.org/hib_docs/v3/re ... n-property
It's not the doc of hib annotations, but annotations normally permits what xml does too.
IMO, what you want to do is not really a unique key constraint, it's more like a "check" constraint : something that you can execute on each insert to check if it's correct.
I don't think dbms provide the ability to specify such a constraint calling it a "unique" one.
So, maybe you could have a look at the column mapping :
http://www.hibernate.org/hib_docs/v3/re ... ing-column
Something like
Code:
<column
name="your_col"
not-null="true"
check="here put your sql verifying that the value of the column is not already used, case insensitive"
/>