A wide range of bis(trimethylsilyl)methyl (BTSM)- substituted heteroaryl derivatives has been prepared by using Kumada-Corriu or Negishi cross-coupling reactions. The regioselective lithiation or magnesiation of these building blocks bearing a bulky BTSM group by using magnesium or lithium 2,2,6,6-tetramethylpiperidide bases followed by quenching reactions with different electrophiles provides various functionalized N-, O-, or S-heterocycles. Furthermore, the BTSM group can then be converted into formyl, methyl, or styryl groups to give access to a variety of highly functionalized heteroaromatics.

Deprotonative metalation of N-isopropenyl-1H-pyrroles with superbases followed by trapping with a variety of electrophiles was studied as an effective tool for the regioselective functionalization of 1H-pyrroles

Preparation and Regioselective Magnesiation or Lithiation of Bis(trimethylsilyl)methyl-Substituted Heteroaryls for the Generation of Highly FunctionalizedHeterocycles. -A wide range of bis(trimethylsilyl)methyl (BTSM)-substituted heteroaryl derivatives is prepared by using Kumada-Corriu or Negishi cross-coupling reactions. The regioselective lithiation or magnesiation of these building blocks bearing a bulky BTSM group by using magnesium or lithium 2,2,6,6-tetramethylpiperidide bases followed by quenching reactions with different electrophiles provides various functionalized N-, O-, or S-heterocycles. The BTSM group can be converted into formyl, methyl, or styryl groups to give access to a variety of highly functionalized heteroaromatics. -(KLATT, T.; WERNER, V.; MAXIMOVA, M. G.; DIDIER, D.; APELOIG, Y.; KNOCHEL*, P.; Chem. -Eur. J. 21 (2015) 21, 7830-7834, http://dx.