Using the formula (n-2)*180 as the sum of interior angles of a polygon:
With n = 5, you get 3*180, or 540.
If all the same (regular) you'll get 540/5 or 108.
To have two equal cuts meet at that angle you'll have to have each 54 degrees.
Most, if not all miters turn only to 45 degrees on the scale, and are initially perpendicular to the blade, so set at the complimentary angle (90 - 54) = 36 degrees.
Dan (not a cabinetmaker)