Synthesis of unsymmetrical dialkoxydiarylsilanes and diarylsilanediols from tetraalkoxysilane having a dioxasilepane unit.

The tetraalkoxysilane carrying a stable seven-membered dioxasilepane moiety and two trifluoroethoxy groups undergoes reliable iterative substitution of the two trifluoroethoxy groups by sequential treatment with different aryl Grignard reagents while keeping the seven-membered structure intact. The process results in the synthesis of unsymmetrical dialkoxydiarylsilanes and eventually diarylsilanediols after proper hydrolysis.

Sodium silylsilanolate as a precursor of silylcopper species.

Silylcoppers function as convenient and effective sources of silicon functional groups. Commonly used precursors for those species have been limited to certain symmetric disilanes and silylboranes. This fact renders the development of silylcopper precursors desirable so that more diverse silyl groups could be efficiently delivered.

Sodium silylsilanolate enables nickel-catalysed silylation of aryl chlorides.

Structurally diverse aryl chlorides were silylated with sodium silylsilanolate reagents in the presence of a Ni(cod)2 catalyst complexed with a phosphine ligand; PMe2Ph for electron-rich substrates, and PCy2Ph for electron-deficient ones. The mild reaction conditions allowed the silylation of various aryl chlorides including functionalised drug molecules.