AFAIK there isn't an annotation to do this. You have two options
One, create a custom validator annotation. Here is a very good example. Make a call to your DAO class and check the availability in the validator implementation
public boolean isValid(String object, ConstraintValidatorContext constraintContext) {
return userDAO.userNameAvailable(object); //some method to check username availability
}
OR
Set unique = true on your property in your entity class.
@Column(unique = true)
private String userName;
But this will not work with @valid, instead throw an exception on persistence. You have to use an appropriate logic to handle that.
The first solution isn't fool proof. Check this answer on SO.
The second will will never fail.
UPDATE
As NimChimpsky commented, using both together will be a concrete solution.