For the caramel and fruit: Stir the sugar and 1 1/2 tablespoons water together in a 10-inch ovenproof skillet to make a mixture like wet sand. Cook over medium-high heat until melted and light amber, about 5 minutes. Stir in the salt if making a salted caramel. Arrange the peaches, cut-side down, on top. Drizzle the bourbon over the fruit.
For the batter: Whisk together the flour, pecans, baking powder, baking soda and salt in a medium bowl.
Beat together the sugar and butter in a large bowl with an electric mixer on medium-high speed until light and fluffy, about 3 minutes. Add the eggs, 1 at a time, beating after each addition, then beat in the vanilla. Reduce the speed to low and add the flour mixture in 3 batches, alternating with the buttermilk, stirring until just incorporated.
Pour the batter over the fruit and spread evenly. Bake until golden brown all over and a toothpick inserted into the center of the cake comes out clean, about 50 minutes. Let rest for 15 minutes and then invert onto a platter. Cool to room temperature before serving. Serve with scoops of vanilla ice cream if using.
When measuring flour, we spoon it into a dry measuring cup and level off the excess. (Scooping directly from the bag compacts the flour, resulting in dry baked goods.)
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