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Arrange a rack in the center of the oven and preheat to 350°.
In a large bowl, whisk together sugar, corn starch, zest, salt, and cinnamon until completely combined. Add peaches and toss to coat. Set aside while you prepare the topping. Pour melted butter into a 12-inch cast iron skillet.
In a medium bowl, whisk together flour, sugar, baking powder, and salt. Add butter and toss to break up the pieces, then smash each one flat between your fingertips. Continue smashing and rubbing until butter is broken up into small pieces like cereal flakes. Stir in buttermilk with a flexible spatula.
Scrape into a prepared skillet and drop the thick dough in 1-tablespoon portions over the fruit spaced evenly apart. Sprinkle with additional sugar for crispier tops.
Place on a foil-lined sheet pan and bake until the biscuits are golden brown and the fruit is bubbling hot in very center, about 1 hour. Cool at least an hour before serving, to allow the filling to thicken (while piping hot, it will be runny and thin).