1Heat oven to 350°F. Place paper baking cup in each of 24 regular-size muffin cups. In large bowl, beat cake mixes, butter, water, vanilla and eggs with electric mixer on low speed 30 seconds, then on medium speed 2 minutes, scraping bowl occasionally. Divide batter evenly among muffin cups, filling each three-fourths full.
2Bake 20 to 25 minutes or until toothpick inserted in center comes out clean. Cool 5 minutes; remove from pan to cooling rack. Cool completely, about 30 minutes.
3In large bowl, beat whipping cream with electric mixer on high speed until stiff. Add mascarpone cheese, 3 tablespoons liqueur, cold brewed coffee and the powdered sugar; beat just until well blended and thick enough to pipe or spread (do not overbeat).
4In shallow bowl, place 1/4 cup liqueur. Dip tops of each cooled cupcake into liqueur. Top with whipped cream mixture. Sprinkle with cocoa and chocolate shavings. Store loosely covered in refrigerator.