Palladium-Catalyzed Synthesis and Transformations of Organometallic Compounds

Abstract: This thesis is focused on two important fields of palladium catalysis: the development of electrophilic allylic substitution reactions via bis-allylpalladium intermediates; and application of palladium pincer-complexes in the synthesis and transformations of organometallic compounds.Palladium-catalyzed electrophilic allylation of aldehyde and imine substrates could be achieved using readily available allyl chlorides and acetates by employing hexamethylditin or bis(pinacolato)diboron reagents. The reaction proceeds under mild and neutral reaction conditions with high regioselectivity, providing the branched homoallylic products. The stereoselectivity of the reaction depends on the steric and electronic effects of the allylic substituents of the substrates. DFT modeling of the electrophilic attack on the bis-allylpalladium intermediate of the reaction revealed the origin of the regio- and stereoselectivity of the reaction.Palladium pincer-complexes were employed as catalysts in a variety of reactions such as stannylation, selenylation, allylation, and cross coupling reactions with various electrophiles. Allylic stannylation in the presence of hexamethylditin was achieved by use of an NCN palladium pincer-complex catalyst. In contrast to the reactions catalyzed by traditional palladium catalysts, isolation of functionalized allyl stannanes was possible due to the special features of the pincer-complex catalyst. Extension of the scope of the palladium pincer-complex catalyzed electrophilic allylation reactions was achieved by using potassium trifluoro(allyl)borate instead of allyl stannanes. In addition, asymmetric electrophilic allylation of sulfonimines was achieved by employment of novel BINOL-based palladium pincer-complexes. The enantioselectivity of the pincer-complex catalyst was fine-tuned by employment of substituted analogs of BINOL.