Palladium‐Catalyzed Hydroformylation of Alkenes and Alkynes

Hydroformylation of alkenes and alkynes with syngas represents a method of choice to furnish valuable aldehydes with the 100 % atom‐economy from readily available building blocks. The field is dominated by Rh‐ and Co‐catalysis; however, complexes of many other metals were also shown to be catalytically competent. Here we review the studies of hydroformylation under Pd‐catalysis, starting from the seminal reports up to the most recent examples. Special emphasis is paid to the unique regio‐ and chemoselectivities of Pd‐based methods, which are difficult to achieve with the conventional hydroformylation protocols. Different mechanistic proposals are presented along with a summary of their experimental and computational support. Finally, the user‐friendly methods using surrogates of syngas are discussed as well. Overall, the Minireview aims to present unique opportunities and remaining challenges of Pd‐catalyzed hydroformylation reactions for their prospective applications in fine‐chemical synthesis. The development of the field of the Pd‐catalyzed hydroformylation of alkenes and alkynes, from the seminal studies up to the current state of the art, remaining challenges, different mechanistic proposals involving unusual features as well as unique synthetic opportunities inaccessible with conventional Rh‐catalysis, are discussed.