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, toss the diced rhubarb with ½ cup granulated sugar and 2 tablespoons melted butter until the fruit 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 mixing bowl, whisk together the flour, remaining ½ cup sugar, baking powder, baking soda, and salt until well distributed.
04 - In a separate bowl, whisk the cooled melted butter, egg, buttermilk, and vanilla extract until smooth and fully incorporated.
05 - Pour the wet mixture into the dry ingredients. Using a spatula, fold gently just until no dry pockets of flour remain. Avoid overmixing to keep the muffins tender.
06 - Divide the batter evenly among the prepared muffin cups, spooning it directly over the rhubarb layer in each well. Fill each cup about three-quarters full.
07 - Bake on the center rack for 22 to 25 minutes, rotating the pan halfway through, until a toothpick inserted into the center of a muffin comes out clean and the tops are golden.
08 - Let the muffins rest in the pan for 5 minutes. Run a butter knife around the edges of each muffin to loosen, then carefully invert the entire pan onto a wire rack. The caramelized rhubarb layer should now be on top. Serve slightly warm or at room temperature.