Sulfonyloxylation and Acetoxylation of Aryl C-H Proximal to a λ3-Iodanediyl Group on Biaryl Structures

lambda 3-Iodane-mediated proximal aryl C-H sulfonyloxylation and acetoxylation on 2-iodo-1,1-biphenyl structures have been achieved. Intramolecular electron transfer between cationic I(III) and proximal 2-Ar groups in 2-arylphenyl-lambda 3-iodanes is a key step to generate the iodanyl radical intermediate with a radical cationic Ar moiety that undergoes the nucleophilic addition of acetate or sulfonate. Electron spin resonance experiments supported the proposed mechanism. A 2-benzyl-iodobenzene structure was also applicable to this reaction system.

Automated summary

Proximal aryl C-H sulfonyloxylation and acetoxylation on 2-iodo-1,1-biphenyl structures have been achieved using λ3-iodane as a catalyst. The key step in this reaction involves intramolecular electron transfer between cationic I(III) and proximal 2-Ar groups in 2-arylphenyl-lambda 3-iodanes, leading to the generation of an iodanyl radical intermediate with a radical cationic Ar moiety. This intermediate then undergoes nucleophilic addition of acetate or sulfonate. The proposed mechanism is supported by electron spin resonance experiments. A 2-benzyl-iodobenzene structure is also compatible with this reaction system.