Manganese(III) porphyrin-catalyzed regioselective dual functionalization of C(sp3)-H bonds: the transformation of arylalkanes to 1,4-diketones.

The first, direct way from arylalkanes to 1,4-dicarbonyl compounds has been shown. It makes obtaining these useful products more accessible and cheaper. Our method is based on a one-pot reaction with excellent regioselectivity, mild conditions, and water as the main solvent. A plausible reaction mechanism has also been proposed.

Pd-Catalyzed Boroperfluoroalkylation of Alkynes Opens a Route to One-Pot Reductive Carboperfluoroalkylation of Alkynes with Perfluoroalkyl and Aryl Iodides.

A three-component tandem Pd-catalyzed perfluoroalkylative borylation of terminal and internal alkynes is presented. On the basis of this methodology, the first reductive dicarbofunctionalization of alkynes with two electrophiles (perfluoroalkyl and aryl iodides) through a temperature-controlled sequence of iodoperfluoroalkylation-borylation coupling is developed. This regio- and stereoselective process is easily controllable by a temperature program, providing access to fluoroalkyl-substituted vinyl iodides, vinyl boronates, or olefins from the very same complex reaction mixture (four substrates, catalysts, base, and additives).

Tandem Palladium-Catalyzed 6- exo- dig Oxocyclization Coupling of δ-Acetylenic ß-Ketoesters with Aryl Bromides and Chlorides: Route to Substituted Dihydropyrans.

We report an efficient and functional group-tolerant method for the synthesis of substituted dihydropyrans, based on tandem Pd-catalyzed cyclization/coupling of δ-acetylenic ß-ketoesters with aryl halides. The reaction proceeds cleanly through 6- exo-dig oxocyclizaton mode, delivering products with very good yields and complete control of regio- and stereoselectivity. Due to mild conditions, the transformation offers exceptional tolerance of functionalities, including NHR, formyl, enolizable ketone, free OH and NH2 groups, as well as a range of N-heterocyclic moieties of potential biological relevance.

Pd-Catalyzed Carbonylative Carboperfluoroalkylation of Alkynes. Through-Space 13C-19F 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 13C-19F couplings, accessible through the analysis of routine 13C NMR spectra.