Rapid Access to Dispirocyclic Scaffolds Enabled by Diastereoselective Intramolecular Double Functionalization of Benzene Rings

Here we describe the diastereoselective synthesis of (5r,8r)‐1,9‐diazadispiro[4.2.48.25]tetradecatrienes via domino double spirocyclization of N‐arylamide derivatives. This reaction can serve as a fast way to synthesize diazadispirocycles, which are found in the core structures of bioactive natural products. Product diversification via Suzuki–Miyaura cross coupling and application to the synthesis of 1‐oxa‐9‐azadispiro[4.2.48.25]tetradecatrienes were also conducted.