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.