Butter a baking sheet and set aside. Bring the sugar, dark corn syrup and 1 cup water to a boil in a medium saucepan over medium heat, stirring occasionally. Cook until a candy thermometer registers 260 degrees F. Stir in the butter and all the cashews and continue to cook until the cashews are well coated and not clumpy, about 3 minutes. Stir in the baking soda and five-spice powder. Pour onto the prepared baking sheet and spread into a thin, even layer. Let cool for 15 minutes, then top with the white chocolate and let sit until the chips are soft and spreadable. Spread into a smooth layer.
Put the chiles and peppercorns into a small skillet over medium heat and toast until fragrant, about 2 minutes. Sprinkle evenly over the white chocolate and let set completely, about 3 hours, then break into pieces.
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