Alcohol Synthesis by Cobalt-Catalyzed Visible-Light-Driven Reductive Hydroformylation.

A cobalt-catalyzed reductive hydroformylation of terminal and 1,1-disubstituted alkenes is described. One-carbon homologated alcohols were synthesized directly from CO and H 2 , affording anti-Markovnikov products (34-87% yield) with exclusive regiocontrol (linear/branch >99:1) for minimally functionalized alkenes. Irradiation of the air-stable cobalt hydride, (dcype)Co(CO) 2 H (dcype = dicyclohexylphosphinoethane) with blue light generated the active catalyst that mediates alkene hydroformylation and subsequent aldehyde hydrogenation. Mechanistic origins of absolute regiocontrol were investigated by in situ monitoring of the tandem catalytic reaction using multinuclear NMR spectroscopy with syngas mixtures.