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Preheat oven to 300°F. Remove all unpopped kernels from popped popcorn. In a large baking or roasting pan, combine popcorn, cereal, pretzels and pecans.
In a medium saucepan, combine brown sugar, butter and corn syrup. Cook and stir with a wooden spoon over medium heat until mixture boils. Reduce heat to medium-low. Cook without stirring for 5 minutes more. Remove pan from heat. Stir in pumpkin pie spice, baking soda, vanilla and cayenne. Pour over the popcorn mixture in pan, gently stirring to coat.
Bake for 15 minutes. Stir mixture; bake 5 minutes more. Spread caramel corn mixture on a large piece of buttered foil to cool. Break into pieces. Store tightly covered for up to 1 week.