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Bah. Still not getting it. This might be a 2-dayer/sleep-on-itter for me.

I can easily imagine a Rubik's cube with the 24 3 letter answers on the outer edges. No problem there.

But if that's the case why does the preamble describe 2 cubes?

How can the sandwich filling have four black squares, then, miraculously, just the one, when I imagine it in the round?

Don't try to help me. I'm beyond help and have already cracked open a soothing drink.

Panga as a bear with a sore head with myself....

ps please do enjoy your well-deserved smugness, the finishers, to whom I proffer my agonies as a sauce

Pendragon.
The five comes in because there are four 3×3 blocks, one in each corner, which describe the top and bottom faces of the two cubes. The fifth is the middle slice, which is common to both cubes, as stated in paragraph 3 of the instructions.

My reading of the instructions suggests that, if you take the four 3x3 corners, you should be able to substitute the two middle row letters in each for other letters to give eight new definitions of the eight unentered synonyms. Clearly not!