Deoxygenative Intramolecular Minisci‐Type Reaction to Access Fused Heterocyclic Scaffolds

Herein, we present a straightforward strategy for the synthesis of fused heterocycles through a deoxygenative, intramolecular Minisci‐type reaction. This approach grants access to complex polycyclic scaffolds in three steps from readily available starting materials, such as chlorinated heteroarenes and 1,3‐diols. The use of saccharide derivatives as the starting 1,3‐diol motif allows for the synthesis of novel heterocyclic scaffolds with excellent diastereoselectivity and formal retention of configuration at the newly formed C−C bond. Rapid build of molecular complexity is a key for the development of novel bioactive molecules. Herein we present a three‐step synthetic sequence to access fused heterocyclic scaffolds from readily available starting materials, such as halogenated heteroarenes and 1,3‐diols. The key step of the strategy is the development of a deoxygenative intramolecular Minisci‐type reaction.