Well, if you know for sure that the key exists, then you can simply do:
$to = $array[$email];
But here are two better ways that check whether the key is there first:
$array = ('Mr. President' => 'someone@domain.com');
$email = 'Mr. President';
if (isSet($array[$email]))
$to = $array[$email];
else
$to = ''; // Not found
Another way:
$array = ('Mr. President' => 'someone@domain.com');
$email = 'Mr. President';
$key = array_search($email, $array);
if (FALSE === $key)
$to = ''; // Not found
else
$to = $array[$key];
EDIT:
Posted too late. Oh well, you get another example/ways to do the same thing.