01 - Preheat oven to 375°F. Grease a standard 12-cup muffin tin generously with butter or line with paper liners.
02 - In a medium bowl, combine the diced rhubarb, ½ cup granulated sugar, and 2 tablespoons melted butter. Toss until the rhubarb is evenly coated. Spoon a heaping tablespoon of the mixture into the bottom of each muffin cup, pressing lightly to form an even layer.
03 - In a large bowl, whisk together the flour, remaining ½ cup sugar, baking powder, baking soda, and salt until well distributed.
04 - In a separate bowl, whisk together the cooled melted butter, egg, buttermilk, and vanilla extract until smooth and homogeneous.
05 - Pour the wet ingredients into the dry ingredients. Fold gently with a spatula just until combined — a few small lumps are fine. Overmixing will produce tough muffins.
06 - Divide the batter evenly among the 12 muffin cups, spooning it directly over the rhubarb layer. Fill each cup about three-quarters full.
07 - Bake for 22 to 25 minutes, rotating the pan halfway through, until the muffin tops are golden and a toothpick inserted into the center comes out clean.
08 - Let the muffins cool in the pan for 5 minutes. Run a butter knife around the edge of each muffin to loosen, then place a wire rack over the pan and invert. The rhubarb topping should now be on top. Serve slightly warm or at room temperature.