Recently, the Zhang Feng Group of Chongqing University published an article in Angewandte Chemie International Edition entitled "Thioethers as Dichotomous Electrophiles for Site-Selective Silylation via C−S Bond Cleavage".

Aryl alkyl sulfides are widely found in natural products, pharmaceutical molecules and materials. The development of aryl alkyl sulfides as dichotomous electrophiles for site-selective silylation via C-S bond cleavage has been achieved. Iron-catalyzed selective cleavage of C(aryl)-S bonds can occur in the presence of β-diketimine ligands, and the cleavage of C(alkyl)-S bonds can be achieved by t-BuONa without the use of transition metals, resulting in the corresponding silylated products in moderate to excellent yields, scaled up to gram scale, and can be applied for the late silylation of natural medicine molecules and natural bioactive derivatives. In addition, the authors have achieved the silylation of secondary aryl alkyl sulfides, which may provide promising application value in the medicinal chemistry. Mechanistic studies suggest that Fe-Si species may undergo metathesis reactions during the cleavage of C(aryl)-S bonds, while silyl radicals are involved during the cleavage of C(alkyl)-S bonds.

Related link: https://onlinelibrary.wiley.com/doi/10.1002/anie.202303470