Search Results (6)

The presented studies aimed to evaluate the peripheral coordinating properties of a novel porphyrinoid family representative preceded by its synthesis for potential sensing purposes. Two synthetic pathways were employed to a obtain maleonitrile derivative, further used as a starting material in the cyclotetramerization reaction. In the first one, DAMN was used in sequential double-reductive alkylation with 2-thiophene-carboxyaldehyde and sodium borohydride. In the second, DAMN was used in a one-pot reaction with 2-thiophene-carboxyaldehyde in the presence of a 5-ethyl-2-methylpyridine borane complex in methanol and acetic acid. Following the Linstead approach, the cyclization reaction led to a novel symmetrical magnesium(II) octaaminoporphyrazine with methyl(2-thiophenylmethylene) substituents. The macrocycle’s electrochemical properties were assessed by cyclic and differential pulse voltammetries revealing one reduction and two oxidation peak potentials. The additional spectroelectrochemical measurements showed formation of a cationic form of the macrocycle at an applied potential of 0.6 V. The coordinating properties due to the palladium ion of novel porphyrazines were measured with the use of titration combined with UV–vis spectrometry. The titration of Pd²⁺ revealed the good sensing activity of porphyrazine in the range of 0.1 to 5 palladium molar equivalents. In addition, Pd²⁺ ions coordination was also assessed by electrochemical studies, indicating the peak potential shift of 0.1 V in the presence of metal cations. DFT calculations showed the good agreement between theoretical and experimental data in the UV–vis and ¹H NMR studies. Full article

Ni catalysis constitutes an active research arena with notable applications in diverse fields. By analogy with its parent element palladium, Ni catalysts provide an appealing entry to build molecular complexity via cross-coupling reactions. While Pd catalysts typically involve a M⁰/M^II redox scenario, in the case of Ni congeners the mechanistic elucidation becomes more challenging due to their innate properties (like enhanced reactivity, propensity to undergo single electron transformations vs. 2e⁻ redox sequences or weaker M–Ligand interaction). In recent years, mechanistic studies have demonstrated the participation of high-valent Ni^III and Ni^IV species in a plethora of cross-coupling events, thus accessing novel synthetic schemes and unprecedented transformations. This comprehensive review collects the main contributions effected within this topic, and focuses on the key role of isolated and/or spectroscopically identified Ni^III and Ni^IV complexes. Amongst other transformations, the resulting Ni^III and Ni^IV compounds have efficiently accomplished: i) C–C and C–heteroatom bond formation; ii) C–H bond functionalization; and iii) N–N and C–N cyclizative couplings to forge heterocycles. Full article

A palladium-catalyzed synthesis of the carbazole framework is described, including the preparation of 2-, 5-, and 7-oxygenated natural and unnatural carbazole alkaloids. A series of N-arylcyclohexane enaminones, generated by condensation of cyclohexane-1,3-dione with diverse anilines, were aromatized by a Pd(0)-catalyzed thermal treatment to afford the corresponding diarylamines. The latter were submitted to a Pd(II)-catalyzed cyclization and methylation processes to provide the desired carbazoles, including clausine V. Following an inverse strategy, a new and short total synthesis of glycoborine is also reported. Full article