I had a meeting this past summer with a venue that specializes in food and wine/spirits pairing. The owner does classes, etc. She recommended pairing my Sugar 'n' Spice cake with aged rum, so maybe a spiced buttercream? I use fairly traditional spices in it...cinnamon, nutmeg, cloves.
Coconut or even a simple vanilla bean goes beautifully with rum. I made a vanilla bean rum buche de noel last Christmas and it was awesome. I flavored French buttercream with rum and vanilla bean paste and everyone loved it.
If you wanted to try something different, rather than the standard coconut or vanilla, you could do a search for flavored rum. Any of the flavors that they already mix with rum should pair rather well with rum flavored cupcakes. Bacardi does pineapple, different berries, and melon to name just a few.
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