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Preheat oven to 350°F. Coat an 8-inch-round cake pan with cooking spray. Line bottom with wax or parchment paper; coat paper.
In small bowl, whisk together flour, salt and baking soda; set aside.
Microwave 8 ounces chocolate and butter in a medium microwave-safe bowl for 1 minute, stirring halfway through; microwave for another 15 seconds if necessary and stir until smooth. Whisk in sugar and vanilla, then stir in eggs, buttermilk and 2/3 cup walnuts until well blended. Stir in flour mixture until just combined.
Pour batter into prepared pan. Bake for 60 to 65 minutes or until a toothpick inserted in the center tests clean. Remove to a wire rack and cool in pan 5 minutes, then invert pan onto wire rack and cool completely. Remove and discard wax paper.
Place the remaining 4 ounces chocolate in small bowl. Heat cream in a saucepan over medium heat until just simmering. Pour over chocolate. Let stand 4 minutes to melt; stir until smooth.
Place cake on a wire rack over a baking sheet. Pour glaze over cake; use a spatula to smooth over top and sides. Pat the remaining 1/3 cup walnuts around the top. When the glaze is firm, remove cake to a platter and serve.