Straightforward Stereoselective Synthesis of Seven-Membered Oxa-Bridged Rings through In Situ Generated Cycloheptenol Derivatives

An iodine-mediated stereoselective synthesis of seven-membered oxa-bridged rings via in situ generated cycloheptenols was reported. This process was realized through the combination of C–C σ-bond cleavage and C–O bond-forming reactions in a one-pot fashion from simple and easily accessible raw materials. The formation of carbon radicals initiated by I2 was the key to the reaction.