Rename the CAfile to cert.pem since that's the hardcoded default.

$ strings ~/.rbenv/versions/2.0.0-rc2/openssl/lib/libcrypto.a |
  grep -B3 SSL_CERT_FILE
/Users/jeremy/.rbenv/versions/2.0.0-rc2/openssl/ssl/certs
/Users/jeremy/.rbenv/versions/2.0.0-rc2/openssl/ssl/cert.pem
SSL_CERT_DIR
SSL_CERT_FILE