Studies on the Total Synthesis of Hirtellanine A: Regioselective Synthesis of Benzopyran

The total synthesis of Hirtellanine A was accomplished by two different synthetic approaches. Hirtellanine A was assembled using a one‐pot, tandem acid‐mediated deprotection and tautomerization cascade starting from quinone derivative 23 . The key features of the synthesis include a Houben–Hoesch reaction of aryl cyanide 3 with phloroglucinol, a one‐pot sequential boronation, a Suzuki–Miyaura cross‐coupling of aryl bromide 33 with aryl iodide 26 , and a base‐mediated regioselective Claisen rearrangement for the benzopyran construction.