Reductively disilylated N-heterocycles as versatile organosilicon reagents

Abstract

The reductively disilylated N-heterocyclic systems 1,4-bis(trimethylsilyl)-1-aza-2,5-cyclohexadiene (1Si), 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine (2Si) and its methyl derivatives (3Si and 4Si), and 1,1′-bis(trimethylsilyl)-4,4′-bipyridinylidene (5Si) are proficient organosilicon reagents owing to their low first vertical ionization potentials and the heterophilicity of the polarized N–Si bonds. These have prompted their reactivity as two-electron reductants or reductive silylations. These reactions benefit from the concomitant rearomatization of the N-heterocycles and liberation of trimethylsilyl halides or (Me3Si)2O, which are mostly volatile or easily removable byproducts. In this perspective, we have discussed the utilization of these reductively disilylated N-heterocyclic systems as versatile reagents in the salt-free reduction of transition metals (A) and main-group halides (B), in organic transformations (C) and in materials syntheses (D).