Enantioselective semireduction of allenes.

Abstract

Rh-hydride catalysis solves a synthetic challenge by affording the enantioselective reduction of allenes, thereby yielding access to motifs commonly used in medicinal chemistry. A designer Josiphos ligand promotes the generation of chiral benzylic isomers, when combined with a Hantzsch ester as the reductant. This semireduction proceeds chemoselectively in the presence of other functional groups, which are typically reduced using conventional hydrogenations. Isotopic labelling studies support a mechanism where the hydride is delivered to the branched position of a Rh-allyl intermediate.Reduction of allenes poses several challenges in terms of chemo-, regio- and enantio-selectivity. Here, the authors report a rhodium-Josiphos catalytic system that reduces a variety of aryl allenes to chiral benzylic compounds with excellent selectivity and functional group tolerance.