No, if you have a dual-homed stack right now, and they only expose IPv4, you connect over IPv4, you don't attempt to connect over IPv6 and get connection denied.

That's rather the problem - there's no trivial way to mimic that policy transparently while enabling IPv6, because most stacks will default to using IPv6 if they're dual-homed and expose both, and won't fall back if IPv6 connects but gives an error. (Offhand, I think the best you could do would be to tell everyone that you're migrating to a new URI scheme to allow cloning, with IPv6 enabled, and that as part of that, you'll have to update your allow/deny rules, then, after a truly astonishingly long time and lots of nagging of anyone who never does it, make the old path an alias of the new one and let the last remaining people break.)