Aminomethylations of electron-deficient compounds-bringing iron photoredox catalysis into play

The α-functionalisation of N -containing compounds is an area of broad interest in synthetic chemistry due to their presence in biologically active substances among others. Visible light-induced generation of nucleophilic α-aminoalkyl radicals as reactive intermediates that can be trapped by electron-deficient alkenes presents an attractive and mild approach to achieve said functionalisation. In this work, [Fe( iii )(phtmeimb) 2 ]PF 6 (phtmeimb = phenyl(tris(3-methylimidazol-2-ylidene))borate), an N-heterocyclic carbene (NHC) complex based on Earth-abundant iron, was used as photoredox catalyst to efficiently drive the formation of α-aminoalkyl radicals from a range of different α-trimethylsilylamines and their subsequent addition to a number of electron-deficient alkenes under green light irradiation. Mechanistic investigations elucidated the different reaction steps of the complete photocatalytic cycle. In terms of yields and substrate scope, we show that [Fe( iii )(phtmeimb) 2 ]PF 6 can compete with noble metal photoredox catalysts, for instance outcompeting archetypal [Ru(bpy) 3 ]Cl 2 under comparable reaction conditions, illustrating that iron photocatalysts can efficiently facilitate photoredox reactions of synthetic value. Electron transfer to the 2 LMCT state of a photoactive complex based on Earth-abundant iron has been used to drive photocatalytic aminomethylation reactions by generation of α-aminoalkyl radicals and the underlying mechanism has been investigated.