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Preheat your oven to 175°C (350°F). Grease four 9-inch round cake pans and line them with parchment paper.
Sift together flour, both cocoa powders, baking soda, baking powder, and salt into a large mixing bowl.
In a separate bowl, whisk together eggs, buttermilk, vegetable oil, sour cream, and vanilla until smooth.
Pour the wet mixture into the dry ingredients and mix until just combined. Slowly stir in the hot espresso.
Divide the batter evenly among your prepared pans, using about 400g per pan. Bake for 18-22 minutes until a toothpick comes out with a few moist crumbs.
Allow the layers to cool in their pans for 10 minutes, then turn them out onto wire racks to cool completely.
Heat heavy cream until just simmering. Pour it over the finely chopped dark chocolate in a large heatproof bowl. Let it sit for 4 minutes, then stir until smooth.
Add butter, corn syrup, and vanilla to the chocolate mixture. Stir until silky and glossy. Cool until it reaches a spreadable consistency.
Transfer 1 cup of ganache to a separate bowl for the exterior coating.
Assemble the cake by spreading ganache filling between each layer.
Refrigerate the assembled cake for 30 minutes.
Warm the reserved ganache and pour it over the top of the chilled cake.
Refrigerate for 1 hour until the ganache coating is set.