1. For the Cakes, preheat oven to 350°F. Generously spray 8 (6-ounce) oven proof coffee cups or ramekins with no stick cooking spray with flour or grease and flour cups. Place on large baking sheet.
2. Mix flour, 2/3 cup of the granulated sugar, 4 tablespoons of the cocoa powder, baking powder, ancho chile pepper, cinnamon and salt in large bowl. Stir in milk, oil and vanilla. (Batter will be stiff.) Spoon evenly into prepared cups. Mix remaining 1/3 cup granulated sugar and 2 tablespoons cocoa powder in small bowl. Sprinkle evenly over batter. Spoon 2 tablespoons boiling water into each cup. (Do not stir.)
3. Bake 15 to 20 minutes or until tops are dry to the touch. Cool cups slightly on wire rack.
4. For the Cocoa Whipped Cream, beat cream and confectioners' sugar in medium bowl with electric mixer on high speed until soft peaks form. Add cocoa powder and vanilla; beat until stiff peaks form. Serve cakes in coffee cups while still warm. Dollop with Cocoa Whipped Cream. Sprinkle with additional cinnamon, if desired.
Make Ahead: Prepare and bake cakes as directed. Store in refrigerator overnight. To reheat cakes, microwave on HIGH 30 to 60 seconds or until heated through.
Test Kitchen Tip: Recipe for Cocoa Whipped Cream can be doubled. Serve remaining whipped cream on other desserts, hot cocoa or coffee beverages.