Preheat oven to 350°F (175°C). Grease two 9-inch round cake pans and line bottoms with parchment paper.
In a large bowl, whisk together flour, sugar, cocoa powder, baking soda, baking powder, and salt.
Add eggs, buttermilk, oil, and vanilla, mixing until well combined.
Stir in hot coffee (or hot water), mixing until smooth. The batter will be thin.
Pour batter evenly between prepared pans and bake for 30-35 minutes until a toothpick inserted in center comes out with a few moist crumbs.
Cool in pans for 10 minutes, then transfer to wire racks to cool completely.
For cream filling, beat butter until fluffy, then add powdered sugar, vanilla, and salt, mixing until smooth.
Fold in marshmallow fluff until well combined.
Once cakes are completely cool, level tops if needed. Place one layer on cake plate and spread cream filling evenly, leaving about 1/2 inch border.
Place second cake layer on top, pressing gently to secure. Refrigerate for about 30 minutes.
For chocolate ganache, heat heavy cream until just simmering. Pour over chocolate chips in a bowl and let stand for 2 minutes. Stir until smooth, then add corn syrup if using.
Allow ganache to cool until slightly thickened but still pourable. Pour over chilled cake, using an offset spatula to guide it down the sides.
Refrigerate finished cake for at least 1 hour before serving to set the ganache completely.