Some of the rebels in Syria have taken over Syrian air defence bases. Unlikely that they have the capability to operate the larger systems but they have used SA-8s.
SA-8 Gecko
SA-2 Guideline
Advanced MANPADs such as SA-24 Grinch have been seen in rebel hands.
Syrian Rebels Have Shoulder-Fired Missiles, and That's Not Good - Popular Mechanics
Strategic SAM Deployment in Syria