Regioselective C(sp ³ )–H Silylation of Methyl Sulfides and 2‐Methylanisoles by Bis(imidazolin‐2‐Iminato) Rare‐Earth Catalysts

The catalytic C(sp 3 )–H silylation of methyl sulfides with hydrosilanes offers a facile and efficient route to silylated sulfide derivatives. However, such transformation has remained largely underexplored to date probably due to the lack of suitable catalysts. Herein, we report a highly regioselective α‐C(sp 3 )–H silylation of methyl sulfides with diarylsilanes catalyzed by a bis(imidazolin‐2‐iminato) scandium alkyl complex. A number of silylated sulfides were obtained in moderate to good yield. Moreover, 2‐methylanisoles were also feasibly coupled with hydrosilanes in the presence of the yttrium analog. The potential utility of these methodologies was demonstrated by scale‐up synthesis and the further transformations of silylated products.