try this:
$key = 'a3';
$arr = [
'a1' => '1',
'a2' => '2',
'a3' => '3',
'a4' => '4',
'a5' => '5',
'a6' => '6'
];
if (isset($arr[ $key ]))
$arr = [ $key => $arr[ $key ] ] + $arr;
result:
array(
'a3' => '3',
'a1' => '1',
'a2' => '2',
'a4' => '4',
'a5' => '5',
'a6' => '6'
)