Base‐Promoted Reaction of Phenols with Spirocylic λ3‐Iodanes: Access to Both 2‐Iodovinyl Aryl Ethers and Diaryl Ethers

Herein, an efficient method for vinyl or aryl C(sp2)−O bond forming to construct both the (Z)‐2‐iodovinyl aryl ethers and diaryl ethers under metal‐, photocatalyst‐ and light‐free condition in one‐step, has been developed. To generate the two desired products, we proposed a SNAr2 reaction of phenol with vinyl aryl iodonium salts intermediates that subsequently lead to the phenyl‐I bond cleavage and phenyl‐O bond formation. We firstly found that the vinyl aryl iodonium salts was formed in situ from the spiro‐cis‐β‐phenol‐VBXs, which was generated between electrophilic spiro‐EBXs and nucleophilic arylols. Trisubstituted alkenes and functionalized diaryl ethers can be afforded from the two desired products. An efficient method for vinyl or aryl C(sp2)−O bond formation to construct both (Z)‐2‐iodovinyl aryl ethers and diaryl ethers through a reactivity between spiro‐EBXs and phenols under metal‐, photocatalyst‐ and light‐free conditions has been developed.