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To prepare cake: Preheat oven to 325°F. Coat 9-inch-round cake pan (straight sided) with cooking spray. Line bottom with wax paper; coat paper with cooking spray.
Beat butter in large bowl with an electric mixer on medium-high until fluffy, 1 minute. Add granulated sugar and brown sugar; beat 3 minutes, until smooth. Beat in eggs, 1 at a time. Add chocolate syrup and vanilla and almond extracts; beat 1 minute. With mixer on low, beat in flour and salt; beat on medium 1 minute. Pour batter into prepared pan.
Bake for 55 to 60 minutes, until a toothpick inserted in the center comes out clean. Let cake cool in pan on a rack for 15 minutes. Turn cake out onto rack; remove paper. Cool completely. Keep cake bottom-side up.
To prepare ganache: Bring cream to a boil in a saucepan. Stir in espresso powder until dissolved. Stir in almond liqueur, if using.
Place chocolate in a medium heatproof bowl. Pour hot cream mixture over chocolate; let stand 1 minute. Stir until very smooth. Cover; refrigerate until a good spreading consistency is reached, 45 minutes.
Place cooled cake on a wire rack placed over a baking pan. (The smooth bottom becomes the top; do not turn it right-side up.) Spread ganache over sides of cake. Then pour ganache over the top of the cake. Spread the ganache evenly over the top.
Before ganache sets, gently press almonds onto the sides of the cake, using enough almonds to just cover the sides. Refrigerate for at least 1 hour or overnight.
To serve, let cake come to room temperature.