Yes. Any zone can be configured as a Master Zone. This means that the zone will automatically turn on and off when other zones are watering.
You can also configure a Master Zone delay.
For troubleshooting purposes, we recommend using your last zone as the master valve (i.e., Zone 6 on a six-zone controller or Zone 12 on a twelve-zone controller). This makes diagnosing Master Zone valve issues a lot easier.
You can find additional details for all the controllers here.