Unprecedented directed lateral lithiations of tertiary carbons on NHC platforms

Deprotonation of the tautomeric mixture of 4-amido-imidazoliums and 4-amino-N-heterocyclic carbenes led to dilithiated dianionic functional NHCs, via an unprecedented regioselective, directed remote lateral lithiation of a tertiary CHMe₂ carbon. DFT calculations support that the nature of products is under thermodynamic control.