I'm late to this discussion and I am sure the original installer with a question has finished his installation. I used this fitting and it failed after about 5 years. It began to leak where the CPVC joins the brass. I recommend using a shark bite. It is a great fitting and easy to replace if it fails. It is available at Home Depot.
I debated replacing leaky copper with copper or CPVC. Subsequently, copper was banned in my town due to an epidemic of pinhole leaks. CPVC is now code for all new construction. I'm glad I went with CPVC. It is much easier to work with and significantly cheaper.
Regarding the configuration question. That will work on an electric water heater. For a gas heater, I recommend galvanized pipe with a couple of turns to create space between the vent pipe and the CPVC. Galvanized pipe>Ball Valve> Shark Bite fitting> CPVC. That space can also be created with the flex pipe recommended by another poster.