$re = '/(?:\G(?!^)|\()[^()\s]*\K\s+(?=[^()]*\.md\))/m';
$str = '[probability space](posts/probability space.md) is ... [Sigma Field](posts/Sigma Field.md)';
$subst = "_";
$result = preg_replace($re, $subst, $str);
echo "The result of the substitution is ".$result;
Please keep in mind that these code samples are automatically generated and are not guaranteed to work. If you find any syntax errors, feel free to submit a bug report. For a full regex reference for PHP, please visit: http://php.net/manual/en/ref.pcre.php