Preheat the oven to 425 degrees F. Spray two 6-ounce ramekins generously with cooking spray and place on a baking sheet.
Microwave the dulce de leche and butter together in a medium microwave-safe bowl until the butter is melted, about 1 minute. Whisk until smooth. Stir in the powdered sugar until well blended. Whisk in the egg and yolk, then add the vanilla. Stir in the flour until you have a smooth batter. Divide between the prepared ramekins.
Bake until the edges of the cakes are firm but the centers are still soft, 11 to 13 minutes. Let stand for 1 minute, then run a butter knife around the edges of the cakes and invert onto individual plates while still warm. Sprinkle with powdered sugar and serve with the ice cream.
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