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Preheat oven to 350º. Lightly spray an 8 or 9-inch round pan with non-stick cooking spray. Line the bottom of the pan with a parchment paper round.
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For the topping, melt butter, mix in brown sugar and cloves.
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Spread into the bottom of an 8-inch cake pan.
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Arrange peaches on top; set pan aside.
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For the cake, combine flour, baking powder, and salt, in a small bowl and set aside.
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Beat butter and sugar together until light and fluffy.
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Add vanilla and eggs, and beat until well combined.
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Stir in buttermilk, and lastly, the flour mixture.
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Spread cake batter on top of peach mixture, and bake in center of oven for 45 minutes or until a toothpick inserted in center comes out clean.