Windows uses where, UNIX systems which to allow to localize a command. Both will return an empty string in STDOUT if the command isn't found.
PHP_OS is currently WINNT for every supported Windows version by PHP.
So here a portable solution:
/**
 * Determines if a command exists on the current environment
 *
 * @param string $command The command to check
 * @return bool True if the command has been found ; otherwise, false.
 */
function command_exists ($command) {
  $whereIsCommand = (PHP_OS == 'WINNT') ? 'where' : 'which';
  $process = proc_open(
    "$whereIsCommand $command",
    array(
      0 => array("pipe", "r"), //STDIN
      1 => array("pipe", "w"), //STDOUT
      2 => array("pipe", "w"), //STDERR
    ),
    $pipes
  );
  if ($process !== false) {
    $stdout = stream_get_contents($pipes[1]);
    $stderr = stream_get_contents($pipes[2]);
    fclose($pipes[1]);
    fclose($pipes[2]);
    proc_close($process);
    return $stdout != '';
  }
  return false;
}