Markovnikov-Selective, Activator-Free Iron-Catalyzed Vinylarene Hydroboration

Two series of structurally related alkoxy-tethered NHC iron­(II) complexes have been developed as catalysts for the regioselective hydroboration of alkenes. Significantly, Markonikov-selective alkene hydroboration with HBpin has been controllably achieved using an iron catalyst (11 examples, 35–90% isolated yield) with up to 37:1 branched:linear selectivity. <i>anti</i>-Markovnikov-selective alkene hydroboration was also achieved using HBcat and modification of the ligand backbone (6 examples, 44–71% yields). In both cases, ligand design has enabled activator-free low-oxidation-state iron catalysis

Iron-catalysed, general and operationally simple formal hydrogenation using Fe(OTf)(3) and NaBH4

An operationally simple and environmentally benign formal hydrogenation protocol has been developed using highly abundant iron(iii) salts and an inexpensive, bench stable, stoichiometric reductant, NaBH(4), in ethanol, under ambient conditions. This reaction has been applied to the reduction of terminal alkenes (22 examples, up to 95% yield) and nitro-groups (26 examples, up to 95% yield). Deuterium labelling studies indicate that this reaction proceeds via an ionic rather than radical mechanism