I don't believe 'Escape' is one of the options. On macOS Sierra, as for every previous version for me, the only choices to remap through the prefPane are "Caps Lock", "Control", "Option", and "Command".
Hence why Seil/KarabinerElements is the first thing I install on a new Mac.
Interesting. It really has, but I didn't see it before.
I was using Karabiner to set caps lock to control AND escape when pressed independently, something extremely useful to use Vim and command line. This doesn't appear to be supported, unfortunately.
And at least for me, the system preference switches simply don't work for my external keyboard (it can't seem to fully understand the difference between an internal keyboard and an external keyboard).