A practical and efficient protocol for the alpha-perfluoroalkylthiolation of (3-ketoesters was developed using perfluoroalkyl sulfoxides as perfluoroalkylthiolating reagents and trifluoromethanesulfonic anhydride (Tf2O) as the activator. A series of alpha-perfluoroalkylthiolated ketone derivatives were synthesized in moderate to good yields under mild conditions. This transformation is compatible with both aromatic and aliphatic (3-ketoesters and features a broad substrate scope. A possible reaction pathway was proposed based on experimental results.

The reductive deoxygenation of alcohols is a valuable transformation for molecular simplification, yet it typically requires external hydrogen donors. We report a hydroxyl proton transfer strategy for the deoxygenative reduction of triarylmethanols, mediated by a Ph3P/ICH2CH2I system under mild conditions. Notably, no external hydrogen source is needed; instead, utilizing only the alcoholic hydroxy hydrogen as the sole hydrogen donor.

Unsymmetrical chiral 1,2-diamines are important motifs widely present in pharmaceuticals, chiral auxiliaries, and ligands/catalysts. A novel and efficient strategy for the modular synthesis of unsymmetrical chiral 1,2-diaryl ethylenediamines via chiral diboron-templated reductive cross-coupling of aldimines has been established. By leveraging both steric and concentration effects, good chemoselectivity and enantioselectivity have been achieved and homocoupling side-reactions are effectively inhibited. The method exhibits good functional group tolerance and scalability, offering a practical and versatile route to unsymmetrical chiral 1,2-diamines.