Make the file that get called on ppp up. i.e. /etc/ppp/ip-up and make it executable.
Use the remote router to select options to run. (It shows under ifconfig as the other end of the point to point interface.)
Example: when link to 192.168.2.0/24 via 192.168.2.1 comes up add a route to 192.168.3.0/24 via it.
/etc/ppp/ip-up
#!/bin/bash
IFNAME="${1}"
LOCALIP="${4}"
REMOTEIP="${5}"
if [[ "${REMOTEIP}" == "192.168.2.1" ]]; then
/sbin/route add -net 192.168.3.0/24 -interface "${IFNAME}"
fi