Regioselective Aromatic Perfluoro-tert-butylation Using Perfluoro-tert-butyl Phenyl Sulfone and Arynes

The selective introduction of perfluoro-tert-butyl group (PFtB, the bulkier analogue of CF3 group) into arenes has long been sought after but remains a formidable task. We herein report the first general synthetic protocol to realize aromatic perfluoro-tert-butylation. The key to the success is the identification of PFtB phenyl sulfone as a new source of PFtB anion, which reacts with arynes in a highly regioselective manner to afford perfluoro-tert-butylated arenes in high yields. The application of the method is demonstrated by the preparation of sensitive 19F-labeled NMR probes with an extraordinary resolving ability.