Photodriven Sm(III)-to-Sm(II) Reduction for Catalytic Applications.

ABSTRACT

The selectivity of SmI2 as a one electron-reductant motivates the development of methods for reductive Sm-catalysis. Photochemical methods for SmI2 regeneration are desired for catalytic transformations. In particular, returning SmIII-alkoxides to SmII is a crucial step for Sm-turnover in many potential applications. To this end, photochemical conditions for reduction of both SmI3 and a model SmIII-alkoxide to SmI2(THF)n are described here. The Hantzsch ester can serve either as a direct photoreductant or as the reductive quencher for an Ir-based photoredox catalyst. In contrast to previous SmIII reduction methodologies, no Lewis acidic additives or byproducts are involved, facilitating selective ligand coordination to Sm. Accordingly, SmII species can be generated photochemically from SmI3 in the presence of protic, chiral, and/or Lewis basic additives. Both the photoreductant and photoredox methods for SmI2 generation translate to intermolecular ketone-acrylate coupling as a proof-of-concept demonstration of a photodriven, Sm-catalyzed reductive cross-coupling reaction.