Synthesis and application of benzyl-TMS derivatives as bench stable benzyl anion equivalents

The regioselective benzylic metalation of toluenes using BuLi/(KOBu)-Bu-t/TMP(H) (LiNK metalation conditions) and subsequent transmetalation to Si by reaction with TMSCl provides a general one-pot procedure for the synthesis of substituted benzyltrimethylsilanes. ArCH2Si(Me)(3) derivatives are bench stable reagents yet can serve as benzyl anion equivalents under mild reaction conditions. Following activation with fluoride they can successfully participate in a wide range of additions to both non-enolizable and enolizable carbonyls. In addition, their use in the synthesis of isochromanones and trifluoromethylated amines is illustrated. The broad synthetic scope and mild practical conditions of use for ArCH2Si(Me)(3) reagents demonstrate their general potential as benzyl anion equivalents. (C) 2013 Elsevier Ltd. All rights reserved.