I don't understand what it doesn't work for you.
# cat /etc/centos-release
CentOS release 6.8 (Final)
# rpm -q libcurl php-cli
# php -r '
> $ch = curl_init();
> curl_setopt($ch, CURLOPT_URL, "https://tlstest.paypal.com/");
> curl_setopt($ch, CURLOPT_SSLVERSION, CURL_SSLVERSION_TLSv1_2);
BTW, if you want to rebuild, you have to rebuild everything, not only libcurl, but also php, so php-devel won't help you.
Desktop: Fedora 25 x86_64 + rpmfusion + remi-test + remi-dev
Laptop: Fedora 24 x86_64 + remi (SCL only)
Hosting Server: CentOS 6.8 x86_64 + EPEL + remi + remi-php70