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Preheat oven to 375°F. Coat a 9-by-13-inch nonreactive baking dish with cooking spray.
To prepare fruit: Combine peaches, brown sugar, 3 tablespoons all-purpose flour and a pinch of salt in a large bowl. Transfer to the prepared baking dish. Drizzle with bourbon (or vanilla). Tightly cover with foil. Bake until the fruit is steaming, 20 to 30 minutes.
To prepare topping: Meanwhile, whisk whole-wheat flour, all-purpose flour, granulated sugar, baking powder, baking soda and salt in a large bowl. Add butter; rub with your fingers or use a pastry cutter until the pieces are smaller in size, but still visible.
When the peaches are steaming, drizzle buttermilk over the flour mixture and stir with a fork until just combined. Dollop the cobbler topping on top of the hot fruit. Lightly brush the dough with buttermilk and sprinkle with coarse sugar.
Bake until golden brown, 35 to 40 minutes more. Let cool at least 15 minutes before serving.