Photocatalytic Generation of Divalent Lanthanide Reducing Agents

[Image: see text] Divalent lanthanide (Ln) compounds are excellent reducing agents with unique reactivity profiles. These reagents are typically used in superstoichiometric amounts, often in combination with harmful additives. Reactions catalytic in Ln(II) reagents that retain the reactivity and selectivity of the stoichiometric transformations are currently lacking due to the absence of effective and selective methods to form reactive Ln(II) species from stable precursors. Here, active Ln(II) is generated from a Ln(III) precursor through reduction by a photoexcited coumarin or carbostyril chromophore, which, in turn, is regenerated by a sacrificial reductant. The reductant can be metallic (Zn) or organic (amines) and can be used in strictly stoichiometric amounts. A broad range of reactions, including C–halogen, C=C, C=X (X = O, N), P=O, and N=N reductions, as well as C–C, C–X (X = N, S, P), and N–N couplings were readily carried out in yields and selectivities comparable to or better than those afforded by the analogous stoichiometric transformations. The reaction outcomes could be altered by changing the ligand or the lanthanide or through the addition of environmentally benign additives (e.g., water). EPR spectroscopy supported the formation of both Ln(II) and oxidized chromophore intermediates. Taken together, these results establish photochemical Ln(II) generation as a powerful strategy for rendering Ln(II)-mediated reactions catalytic.