Palladium(0)/NHC-Catalyzed Reductive Heck Reaction of Enones: A Detailed Mechanistic Study was written by Raoufmoghaddam, Saeed;Mannathan, Subramaniyan;Minnaard, Adriaan J.;de Vries, Johannes G.;Reek, Joost N. H.. And the article was included in Chemistry – A European Journal in 2015.Application of 16879-39-3 This article mentions the following:
We have studied the mechanism of the palladium-catalyzed reductive Heck reaction of para-substituted enones with 4-iodoanisole by using N,N-diisopropylethylamine (DIPEA) as the reductant. Kinetic studies and in situ spectroscopic anal. have provided a detailed insight into the reaction. Progress kinetic anal. demonstrated that neither catalyst decomposition nor product inhibition occurred during the catalysis. The reaction is first order in the palladium and aryl iodide, and zero order in the activated alkene, N-heterocyclic carbene (NHC) ligand, and DIPEA. The experiments with deuterated solvent ([D7]DMF) and deuterated base ([D15]Et3N) supported the role of the amine as a reductant in the reaction. The palladium complex [Pd0(NHC)(1)] has been identified as the resting state. The kinetic experiments by stopped-flow UV/Vis also revealed that the presence of the second substrate, benzylideneacetone 1, slows down the oxidative addition of 4-iodoanisole through its competing coordination to the palladium center. The kinetic and mechanistic studies indicated that the oxidative addition of the aryl iodide is the rate-determining step. Various scenarios for the oxidative addition step have been analyzed by using DFT calculations (bp86/def2-TZVP) that supported the inhibiting effect of substrate 1 by formation of resting state [Pd0(NHC)(1)] species at the cost of further increase in the energy barrier of the oxidative addition step. In the experiment, the researchers used many compounds, for example, 2-Bromo-4,6-dimethylpyrimidine (cas: 16879-39-3Application of 16879-39-3).
2-Bromo-4,6-dimethylpyrimidine (cas: 16879-39-3) belongs to pyrimidine derivatives. The pyrimidine ring system has wide occurrence in nature as substituted and ring fused compounds and derivatives. A Cu-catalyzed and 4-HO-TEMPO-mediated [3 + 3] annulation of commercially available amidines with saturated ketones enables an efficient and facile synthesis of structurally important pyrimidines via a cascade reaction of oxidative dehydrogenation/annulation/oxidative aromatization.Application of 16879-39-3
Referemce:
Pyrimidine | C4H4N2 – PubChem,
Pyrimidine – Wikipedia