Herein, we describe a KO‐t‐Bu catalyzed thiolation of β‐(hetero)arylethyl ethers through MeOH elimination to form (hetero)arylalkenes followed by anti‐Markovnikov hydrothiolation to afford linear thioethers. The system works well with a variety of β‐(hetero)arylethyl ethers, including electron‐deficient, electron‐neutral, electron‐rich, and branched substrates and a range of aliphatic and aromatic thiols.

In this study, we demonstrated that 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene) (t-Bu-P2) catalyzes the defluorinative functionalization reactions of (2,2,2-trifluoroethyl)arenes with alkanenitriles to produce monofluoroalkene products. The reaction proceeds through HF elimination from a (2,2,2-trifluoroethyl)arene to form a gemdifluorostyrene intermediate, which is followed by nucleophilic addition of an alkanenitrile and elimination of a fluoride anion. The catalysis is compatible with a variety of functional groups.