One-Pot Rapid Access to Benzyl Silanes, Germanes, and Stannanes from Toluenes Mediated by a LiN(SiMe 3 ) 2 /CsCl System.

Organo-silanes, germanes, and stannanes are considered to be conducive to the development of cross-coupling reactions because they are stable, nontoxic, and easy to handle. Using feedstock toluenes, one-pot direct benzylic C-H silylations, germylations, and stannylations are developed. Simply combining toluenes, LiN(SiMe 3 ) 2 /CsCl, and R 3 MCl (M = Si, Ge, Sn) generates a diverse array of bench-stable benzyl silanes, germanes, and stannanes (38 examples, 53-90% yields). The syntheses developed here are easy to access on scale.