Ambient Hydrocarbonylation of Olefins Enabled by Visible‐Light

Hydrocarbonylations of olefins are among the most powerful and widely used processes in the fine and bulk chemical industries, allowing convergent assembly of valuable carbonylated molecules from simple feedstocks. However, an inherent contradictive requirement between olefin insertion and CO insertion causes these reactions to be costly and risky to handle harsh conditions (high temperature and pressurized CO). Here, we establish a photocatalytic approach to resolve the conflicts between the competitive olefin and CO insertion, enabling a palladium-catalyzed ambient hydrocarbonylation of olefins under irradiation of visible-light. This versatile, mild and robust platform offers efficient pathways to assemble valuable carboxylic acids, esters, amides, thioesters, and aldehydes under ambient conditions (at room temperature and 1 atm of CO) with excellent regioselectivities through hydroformylation and hydroxycarbonylation, hydroesterification, hydroaminocarbonylation, and hydrothiocarbonylation of simple olefins. Mechanistic studies suggest that concurrent facile olefin insertion and CO insertion via excitation of carbonyl palladium iodide complex is responsible for this activity.