$re = '/^(.*?)([\s:]+)?{([\s\S].*)?.$/m';
$str = 'key:{value}
key:{valu{0}e}
key:{valu
{0}e}
key: {val-u{0}e}
key: {val__[!]
-u{0}{1}e}';
$subst = "$1,$3";
$result = preg_replace($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