Palladium/Brønsted Acid Catalysis for Hydrofunctionalizations of Alkynes: From Tsuji‐Trost Allylations to Stereoselective Methodologies

Alkynes are one of the most abundant feedstocks for chemical transformations. By merging palladium and Brønsted acid catalysts, they are converted into reactive allylmetal species, which become suitable for Tsuji‐Trost functionalizations with complete atom‐economy. This approach, which overcomes the limitations of traditional methods that suffer from the formation of over‐stoichiometric amounts of by‐products, has been disclosed for developing new C−C and C−Het bond forming methodologies. Within this review, we aim to survey the latest advancements in this area including applications in polymer chemistry, deuterium‐labeling and stereoselective catalysis. Palladium catalysts, in the presence of Brønsted acids, enable Tsuji‐Trost functionalizations using simple alkyne derivatives. The in situ formation of transient, electrophilic allyl‐palladium species is the key to promote new catalytic C−C and C−Het bond forming transformations with complete atom‐economy. This reactivity finds many applications including polymer chemistry, deuterium‐labeling and stereoselective catalysis.