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.