Unprecedented directed lateral lithiations of tertiary carbons on NHC platforms

Abstract

Unexpected and unprecedented directed remote lateral lithiation at one CH(CH₃)₂ of the 3-(2,6-di-isopropylphenyl) wingtip took place upon the reaction of functionalised N-heterocyclic carbene-type molecules with excess of LiCH₂SiMe₃, leading to dilithiated dianionic 4-amido-N-heterocyclic carbenes. DFT calculations show that the nature of the isolated species are under thermodynamic control.