Unprecedented directed lateral lithiations of tertiary carbons on NHC platforms

10 mars 2015

In a combined experimental and theoretical study, the group of Prof Braunstein describes an unexpected and novel transformation that occurred when lithiation of anionic amido–N heterocyclic carbenes was attempted and led to lithiation of the CH(CH3)2 attached to one DiPP wingtip of the NHC. This reaction should be of interest to a wide chemical readership because: This is the first case of selective directed lateral remote lithiation, the second only example of the selective directed lateral lithiation yielding a tertiary carbanion, it offers a wide reaction scope and unusual organolithium structures, and it may lead to new NHC-ligand designs (with applications in main- and transition metal-chemistry), novel organic reactivity of NHCs with electrophiles and even development of methods for functionalization of NHCs with other (non-anionic) substituents.

 

The project was partly funded by the FRC.

 

Reference

Andreas A. Danopoulos, Pierre Braunstein, Gilles Frison et al.
Unprecedented directed lateral lithiations of tertiary carbons on NHC platforms

Chem.Commun.,
2015, 51, 3049 ; DOI:10.1039/c4cc08434a