how many feet of baseboard will there bee and will it all be in series or do you plan on multiple zones?
If you intend to put all the baseboard in one loop, I would just run it as a secondary loop. You would just run the pipe from the boiler to the DHW exchanger and back to the boiler. Then in the most convenient place put two tees close together and pump from the first through the baseboard heaters and back into the second. You could do a couple of these if you need to.
This way you can put the pump on a thermostat to control the house temperature.