Palladium-catalyzed carbonylation reactions, in the presence of nucleophiles, serve as very potent tools for the conversion of aryl and alkenyl halides or halide equivalents to carboxylic acid derivatives or to other carbonyl compounds. There are a vast number of applications for the synthesis of simple building blocks as well as for the functionalization of biologically important skeletons. This review covers the history of carbonylative coupling reactions in Hungary between the years 1994 and 2021.
The synthesis of jasmone and related jasmonoids and pyrethroids is described. These types of compounds play a defensive role in plants, and share a cyclopentenone common core, with variations in its side chains. Jasmone, cinerone, allylrethrone and derivatives are synthesized through π-allyl palladium cross coupling of stannane derivatives. By selective hydrogenation dihydrojasmone and dihydrocinerone are also synthesized.
Herein, a palladium-catalyzed semi-hydrogenation of alkynes to E- and Z-alkenes employing EtOH as hydrogenating agents was reported. The selectivity of the reaction system was effectively controlled by ligand/additive and solvent regulation. The use of sodium acetate/triethanolamine (NaOAc/TEOA), THF and (1R,2R)-bis[(2-methoxypheny)phenyl- phosphino]ethane ((R,R)-DIPAMP), CH3CN was critical for the stereoselective semihydrogenation of alkynes. The general applicability of this procedure was highlighted by the synthesis of more than 36 alkenes, with good yields and high stereoselectivities.
Unprecedented tandem allylic alkylation/intermolecular Michael addition was used in the preparation of novel bicyclic azalides. NMR spectroscopy was used not only to unambiguously determine and characterize the structures of these unexpected products of chemical reaction but also to investigate the effect the rigid bicyclic modification has on the conformation of the whole molecule. Thus, some of the macrolides prepared showed antibacterial activity in the range of well-known antibiotic drug azithromycin.