$a = array('a' => 'a1', 'b' => 'a2', 'c' => 'a3', 'd' => 'a4', 'e' => 'a5');
$k = array_keys($a);
$v = array_values($a);
$rv = array_reverse($v);
$b = array_combine($k, $rv);
var_dump($b);
Result:
array(5) {
'a' =>
string(2) "a5"
'b' =>
string(2) "a4"
'c' =>
string(2) "a3"
'd' =>
string(2) "a2"
'e' =>
string(2) "a1"
}