Chemoselective deprotonative functionalization of benzylic C–H bonds is challenging, because the arene ring contains multiple aromatic C­(sp2)–H bonds, which can be competitively deprotonated and lead to selectivity issues. Recently it was found that bimetallic [MN­(SiMe3)2 M = Li, Na]/Cs+ combinations exhibit excellent benzylic selectivity. Herein, is reported the first deprotonative addition of toluenes to Weinreb amides mediated by LiN­(SiMe3)2/CsF for the synthesis of a diverse array of 2-arylacetophenones. Surprisingly, simple methyl benzoates also react with toluenes under similar conditions to form 2-arylacetophenones without double addition to give tertiary alcohol products. This finding greatly increases the practicality and impact of this chemistry. Some challenging substrates with respect to benzylic deprotonations, such as fluoro and methoxy substituted toluenes, are selectively transformed to 2-aryl acetophenones. The value of benzylic deprotonation of 3-fluorotoluene is demonstrated by the synthesis of a key intermediate in the preparation of Polmacoxib.

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(SiMe3)2/CsCl, and R3MCl (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.

The deprotonation of allylbenzene was successfully demonstrated with a catalytic alkali amide base (NaN(SiMe 3 ) 2 ). The deprotonated allyl anion could be trapped by in situ generated N-(trimethylsilyl) aldimines to provide value-added homoallylic amines (39 examples, 68−98% yields) in a one-pot manner with excellent liner selectivity. Compared with the previously reported method for the synthesis of homoallylic amines, this method does not need to use the preinstalled protection groups on the imines, which need to be removed after the reaction to obtain the N−H free homoallylic amine derivatives.