Preheat oven to 350 degrees.
Stir together boiling water, cocoa, and espresso until smooth; let cool. Beat butter at medium speed with an electric mixer until creamy; gradually add sugar, beating well. Add eggs, 1 at a time, beating until blended after each addition. Combine flour and next 3 ingredients; add butter mixture alternately with cocoa mixture, beginning and ending with flour mixture. Beat at low speed until blended after each addition. Stir in chocolate extract.
Place paper baking cups in 2 (12-cup) muffin pans, and coat with cooking spray; spoon batter into cups, filling two-thirds full. Bake for 12 to 15 minutes or until a wooden pick inserted in center comes out clean. Cool in pans on wire racks 10 minutes; remove from pans to wire racks, and cool completely.
To prepare Vanilla Frosting, beat first 4 ingredients at medium speed with an electric mixer until creamy. Gradually add powdered sugar, beating at low speed until blended. Beat at high speed 2 minutes or until creamy. Make 3 cups.
Frost each cupcake with Vanilla Frosting using metal tip no. 12.
To prepare drizzle, cook butter and sugar in a 2-qt. heavy metal saucepan over high heat, stirring occasionally, until mixture is caramel-colored, about 4 to 5 minutes. Remove from heat, and slowly add cream, stirring constantly until blended. Return to heat, and bring to a boil; cook 1 to 2 minutes, stirring occasionally. Cool. Makes about 1 1/2 cups.
To prepare ganache, cook cream in a heavy nonaluminum saucepan over medium heat, stirring often, just until it begins to steam (do not boil); remove from heat. Place chocolate in a glass bowl. Slowly add hot cream to chocolate, beating with a whisk until chocolate melts and mixture is well blended. The mixture will thicken as it cools. Makes about 2 cups.
Drizzle each cupcake with caramel and chocolate, and top each with chocolate jimmies.