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

Abstract

A cobalt-catalyzed reductive hydroformylation of terminal and 1,1-disubstituted alkenes is described. One-carbon homologated alcohols were synthesized directly from CO and H₂, 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)₂H (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 <i>in situ</i> monitoring of the tandem catalytic reaction using multinuclear NMR spectroscopy with syngas mixtures.