I test it on my Synology DS-209+ and YES! It works! There are some inaccurancy in initDebChroot.sh script Alexandre present on his blog according to the tutorial. Right script according to his tutorial might look like this:
mount -o bind /volume1/@local /opt
mount -o bind /dev /opt/dev
mount -o bind /proc /opt/proc
chroot /opt /bin/bash
But there is one unsolved problem. If you "exit" from chroot you are not in your original NAS environment so you have to manually reboot your NAS to get all changes back.