If a VPN is installed, and it is set to Connect On Demand, and I move from an area with Wi-Fi to LTE (such as when I leave the office for the day), the phone will never make the transition from Wi-Fi to LTE unless I either turn on Airplane mode and turn it off, or disable the VPN. Sometimes if I lock the device and unlock it, the transition will work.
I've filed a Radar for this: #28389227
Has anyone else had this issue? it seems to only be affecting iOS 10.0.1. I've tried resetting network settings to no avail