Rhodium(I) catalysts incorporating small bite‐angle diphosphine ligands, such as (Cy2P)2NMe or bis(diphenylphosphino)methane (dppm), are effective at catalysing the union of aldehydes and propargylic amines to deliver the linear hydroacylation adducts in good yields and with high selectivities. In situ treatment of the hydroacylation adducts with p‐TSA triggers a dehydrative cyclisation to provide the corresponding pyrroles. The use of allylic amines, in place of the propargylic substrates, delivers functionalised dihydropyrroles. The hydroacylation reactions can also be combined in a cascade process with a RhI‐catalysed Suzuki‐type coupling employing aryl boronic acids, providing a three‐component assembly of highly substituted pyrroles.

The first examples of ynamide hydroacylation are described. The choice of ligand system determines reaction regioselectivity, resulting in α- and β-enaminones. The latter are transformed into a variety of N-heterocycles.

A rhodium(i) catalyst mediates selective and efficient coupling reactions between arylmethylsulfides and terminal alkynes to provide Sonogashira-like products.

A broad spectrum of aldehyde substrates bearing mostly additional ‐S‐Me functions reacts with propargylic amines in the presence of RHC under modified conditions A), C), D) or E) to produce linear hydroacylation adducts with high selectivity.