Preheat the oven to 350°F (175°C). Butter and flour a 10-inch Bundt pan.
In the bowl of an electric mixer fitted with the paddle attachment, beat the 2 sticks unsalted butter and 2 cups granulated sugar until light and fluffy, about 5 minutes.
Add the 5 large eggs, 1 at a time, mixing after each addition. Then stir in the 1/4 cup finely grated orange zest.
In another bowl, sift together the 3 cups flour, the 1/2 teaspoon baking powder, 1/2 teaspoon baking soda, and 1 teaspoon kosher salt.
In another bowl, combine the 1/4 cup fresh orange juice, 3/4 cup buttermilk, and 1 teaspoon vanilla extract.
Add the flour and buttermilk mixtures alternately in thirds to the creamed butter, beginning and ending with the flour.
Toss the 2 cups semisweet chocolate chunks with the 2 tablespoons flour and add it to the batter. Scrape the batter into the pan and smooth the surface.
Bake the the cake for 45 minutes to 1 hour, until a cake tester comes out clean.
Let the cake cool in the pan on a wire rack for 10 minutes.
Make the orange syrup
Meanwhile, in a small saucepan over medium-low heat, cook the 1/4 cup granulated sugar with the 1/4 cup freshly squeezed orange juice until the sugar dissolves.
Remove the cake from the pan and place it on a wire rack placed on a rimmed baking sheet. Spoon or brush the orange syrup over the cake. Let the cake cool completely.
Make the ganache (optional)
If making the ganache, melt the 8 ounces good semisweet chocolate chips, 1/2 cup heavy cream, and 1 teaspoon instant coffee granules in the top of a double boiler over simmering water until smooth and warm, stirring occasionally. Drizzle over the top of the cake.