On a cutting board, coarsely chop half the chocolate. Transfer to a large bowl, add the coffee and whisk until the chocolate melts. Whisk in 2 tbsp. bourbon.
In another large bowl, combine the mascarpone, confectioners' sugar, heavy cream, vanilla, cinnamon and the remaining 3 tbsp. bourbon. Using an electric mixer on medium speed, beat until fluffy, 1 to 2 minutes. Add the pumpkin puree; mix on medium-low until blended and creamy.
Working with about one-third of the ladyfingers, dip and roll the cookies, one at a time, in the chocolate mixture until soaked but not soggy, 3 to 4 seconds. Arrange in single layers in the bottoms of six 8-oz. glasses, breaking the cookies if needed. Divide one-third of the pumpkin mixture among the glasses, spooning it on top of the cookies and spreading evenly. Grate about one-third of the remaining chocolate evenly over the pumpkin mixture.
Repeat the layers twice more with the remaining cookies, pumpkin mixture and chocolate. Cover and refrigerate for at least 4 hours and up to 2 days. Serve cold.