Pd-Catalyzed Carbonylative Carboperfluoroalkylation of Alkynes. Through-Space C-F Coupling as a Probe for Configuration Assignment of Fluoroalkyl-Substituted Olefins.

A four-component Pd-catalyzed protocol for direct synthesis of perfluoroalkyl-substituted enones is reported. Under mild conditions and low catalyst loading, alkynes, iodoperfluoroalkanes, (hetero)arylboronic acids, and carbon monoxide are assembled into highly elaborate products with good yields and excellent regio- and stereoselectivities. The configuration of the products was confirmed by the observation of through-space C-F couplings, accessible through the analysis of routine C NMR spectra.