Melt 1 tablespoon butter in a small skillet over medium heat; add pecans. Cook 3 minutes or until toasted, stirring often. Set aside, and let cool.
Combine 3/4 cup brown sugar and 2 tablespoons butter in a bowl; beat at medium speed of a mixer 3 minutes.
Add milk and 1 tablespoon bourbon; beat well.
Combine 1 1/4 cups flour, baking powder, cinnamon, and salt; gradually add to sugar mixture, beating well. Spoon batter into an 8-inch square baking pan coated with cooking spray.
Combine remaining 1/4 cup flour, remaining 2 tablespoons bourbon, and 2/3 cup brown sugar in a small bowl; sprinkle over batter. Top with reserved toasted pecans.
Pour boiling water over batter (do not stir).
Bake at 350 for 35 to 40 minutes or until cake springs back when touched lightly in center.