Recent Hydrocarbonylation of Unsaturated Hydrocarbons with Homogeneous Catalyst

Transition metal-catalyzed hydrocarbonylation of unsaturated hydrocarbons constitutes one of the most important homogeneous processes in industry and academia. In this chapter, we summarized the important research progresses on this area in the past five years, which covered the broad range from the in silico mechanistic investigation to the promising application in the valorization of biomass-derived platform molecules. They demonstrated the hydrocarbonylation of unsaturated hydrocarbon as one of the long-lasting thriving frontiers in the development of homogeneous catalysis. Meanwhile, there are four noteworthy directions yet to be broken through: (i) Catalysts based on earth-abundant transition metals are less explored compared to those of precious transition metals, such as rhodium and palladium; (ii) alkene/alkyne is generally used as the substrate, only several examples of selective bis-carbonylation of cumulated and conjugated unsaturated bonds including 1,3-diene to di-carbonyls have been reported; (iii) contrast to the extensively studied (isomerization) hydrocarbonylation of (internal) alkenes to linear carbonyl compounds, the regioselective conversion of (internal) alkenes to branched products has received less attention; (iv) compared to the wider application of nonasymmetric hydrocarbonylation, the enantioselective variant has yet to be intensively explored. Tackling these challenges would facilitate the hydrocarbonylation to be more widely applied in the manufacture of commodity to fine value-added chemicals.