Cut two 8-inch rounds of cooking parchment paper. Place one round in the bottom of the air fryer basket. Spray with cooking spray.
Separate Pillsbury dough into 5 rolls; set icing aside. Place 3 rolls on parchment paper in an air fryer basket, spacing apart. Cover remaining rolls with plastic wrap, and refrigerate.
Set air fryer to 320°F; cook for 12 minutes. Place a large plate over the air fryer basket, and invert. Discard parchment. Carefully transfer cinnamon rolls back to the air fryer, bottom side up. Cook 2 to 4 minutes or until golden brown and rolls are cooked through. Remove from the air fryer; cover loosely with foil to keep warm while cooking the second batch. Repeat for the remaining 2 rolls, and place on the remaining parchment round in the basket of the air fryer. Cook as directed above.
Meanwhile, in a double boiler, melt chocolate with cream, ancho chili powder, and cayenne pepper. Stir constantly until all the chocolate has melted. Place in a serving bowl and set aside.
In a small bowl combine cinnamon and sugar. Sprinkle on top of cinnamon rolls once they are out of the air fryer.