I suppose You want couple signals coming from WG's rectangular ports, and TE01 is exiteded.
The solution adopted in precision coupler is the following:
The coupler is basically build as 2 waveguide with almost 1 common wall.
Il may be the H or the E wall.
1/4 lamda spaced holes provide the coupling.
As the hole diameter is great and as the wall thikness is small, as the coupling il large.
The most easy value of coupling spans from -30 db to - 10 dB.
Larger copling value (i.e. -4 or -7 dB) require largr holes and became machanically and geometrically hard.
Another solution is the "T junction" and its variants:
1) T with central post (i.e. a screw)
2) Y junction with a thin metal foil in the half of H plane
In any case, is hard to get 25 dB of directivity with so large value of coupling.
If you'll find good results, please let me know.