You can achieve that this way:
$arr = array(
'a1'=>'1',
'a2'=>'2'
);
end($arr);
$last_key = key($arr);
$last_value = array_pop($arr);
$arr = array_merge(array($last_key => $last_value), $arr);
/*
print_r($arr);
will output (this is tested):
Array ( [a2] => 2 [a1] => 1 )
*/