It's failing because UniqueEntity needs to be applied against the entity and not an individual field. Called a class constraint. Your best bet is to use validation.yml as described in : http://symfony.com/doc/current/reference/constraints/UniqueEntity.html
However, it should be possible to apply it using setDefaultOptions:
public function setDefaultOptions(OptionsResolverInterface $resolver)
{
$resolver->setDefaults(array(
'constraints' => array(
new UniqueEntity(array('fields' => array('email'))),