Preheat oven to 350ºF.
Butter the bottom of each of the 3 8-inch round cake pans, then line with parchment paper cut to size.
Combine the chopped chocolate and cocoa powder in a medium sized heat-proof bowl.
Add 1 ¾ cups boiling water and whisk until the mixture is totally incorporated. Set aside to cool a bit. (At this point I just wanted to drink this fragrant chocolate mixture!)
In another bowl whisk together the flour, baking soda, and baking powder.
With your electric mixer, beat the sugars and the mayonnaise in large bowl until well blended, about 2-3 minutes.
Add eggs, one at a time, beating well after each addition, then add the egg yolk and beat until well blended.
Beat in vanilla extract.
To the sugar and egg mixture, add ¼ of the flour mixture and blend, then add ⅓ of the chocolate mixture and blend. Continue alternating until everything is well blended. Occasionally scraping down sides of bowl.
Divide the batter evenly among the three cake pans.
Bake cakes until a tester inserted in center comes out clean, about 30-35 minutes.
Cool cakes in pans on racks for 10-15 minutes.
Run a knife between the edge of the cake and the pan to loosen it, then carefully invert the cakes onto racks to cool completely.