The pyrrole imidazole alkaloids have fascinated chemists for decades because of their unique structures. The high nitrogen and halogen contents and the densely functionalized skeletons make their laboratory synthesis challenging. We describe herein an oxidative method for accessing the core skeletons. of two classes of pyrrole-imidazole dimers. This synthetic strategy was inspired by the putative biosynthesis pathways and its development was facilitated. by computational studies. Using this method, we have successfully prepared ageliferin, bromoageliferin, and dibromoageliferin in their natural enantiomeric form.