I recall that google3 switched to -funsigned-char for x86-64 a long time ago.
I suspect if I dug into the archives, I'd find a discussion on cxx@ with some comments about how doing this would result in some esoteric risk. If I was still on the Chrome team I'd go looking and see if it made sense to reraise the issue now; I know we had at least one stable branch security bug this caused.