In a 9 1/2 or 10 inch nonstick oven-proof skillet, mix sugar and 3 tsp water. Boil, swirling pan, about 5 minutes until sugar starts to caramelize and tuns a light honey color. Remove from heat; stir in butter, lemon juice and scnapps until blended. Cool slightly, then arrange peach slices in caramel, overlapping to fit. Heat oven to 350°F
Whisk flour, baking powder, baking soda and spices in small bowl to blend. In medium bowl, with a handheld mixer on medium speed, beat sugar, butter, egg and extracts 3 minutes, or until pale and smooth. On low speed, alternately beat in flour mixture and buttermilk until just blended. Spoon over peaches; spread evenly to edges.
Bake 35-40 minutes until a wooden pick inserted in center of cake comes out clean. Cool in skillet on a wire rack 5 minutes. Run a thin knife around edges of cake to loosen; invert onto serving plate (if any peach slices stick to skillet, replace on top of cake). Serve cake warm or at room temperature.