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

Abstract

Herein, an efficient method for vinyl or aryl C(sp 2 )À 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 S NAr 2 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.

Organohypervalent heterocycles

“…Ethynylbenziodoxoles have also been utilized for radical alkynylation reactions under photoredox conditions. 459,484–496 Besides, several metal-free alkynylation reactions have also been reported for the synthesis of numerous synthetically important targets, including heterocycles. 497–507 Representative examples for metal-catalyzed, photoredox and metal-free alkynylation reactions using EBXs are presented in Scheme 43.…”

Aryl-, Akynyl-, and Alkenylbenziodoxoles: Synthesis and Synthetic Applications

“…The authors assumed that the vinyl aryl iodonium salts B was formed in situ from the spiro-cis-β-phenol-VBXs B, which was generated between electrophilic spiro-EBXs 59 and nucleophilic arylols 112. Very recently, a similar base-promoted metal-, photocatalyst-and light-free reaction of phenols 112 with spirocyclic EBXs 59 has been developed to construct both the (Z)-2iodovinyl aryl ethers 113 and diaryl ethers 114 (Scheme 23b) [130]. To generate the two desired products, the authors proposed a S NAr 2 reaction of phenol 112 with vinyl aryl iodonium salts intermediates C that subsequently leads to the phenyl-I bond cleavage and phenyl-O bond formation.…”

Diversification of Complex Diaryl Ethers via Diaryliodonium Intramolecular Aryl Rearrangement

“…In recent years, diaryliodonium salts have demonstrated significant advantages in the preparation of diaryl ethers either under metal-free conditions or through transition metal-catalyzed reactions . The recent advancements in the structural modification of diaryliodonium salts have enabled the development of new reagents for the construction of diaryl ether frameworks.…”