Paraformaldehyde and Methanol as C₁ Feedstocks in Metal‐Catalyzed CC Couplings of π‐Unsaturated Reactants: Beyond Hydroformylation

Abstract

Ruthenium-catalyzed reductive couplings of paraformaldehyde with dienes, alkynes, and allenes provide access to products of hydrohydroxymethylation that cannot be formed selectively under the conditions of hydroformylation. In certain cases, the regioselectivity of the CC coupling can be inverted by using nickel catalysts. With iridium catalysts, methanol engages in redox-neutral regioselective hydrohydroxymethylations.