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Copper catalyzed 1,2-diol promoted amination at electron-rich C-5 position of unprotected 2-amino/2-hydroxy-5-halopyridine and selective amination at C-5 in 2-bromo-5-iodopyridine provided excellent yields.
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... Copper-catalyzed reactions of alkynes have advanced significantly over the past few decades, and several useful reviews have been published on the chemistry of alkynes with copper metal. [33][34][35][36][37][38][39] In recent years, studies have been carried out on catalysts based on mesoporous materials doped with rare earth elements (REEs). In studies devoted to the influence of the promoting activity of various nature metals, in particular, when comparing the activity of REEs and d-elements, it was found that the catalyst doped with REE had the best performance. ...
The selective hydrogenation of 1‐hexyne/1‐hexene mixture in the temperature range 100–140°C and a hydrogen pressure of 3 atm was studied on catalysts based on mesoporous silica gel modified with copper and mesoporous silica gel doped with dysprosium and modified with copper. The physicochemical characteristics of the samples were studied by low temperature nitrogen adsorption–desorption method, scanning electron microscopy (SEM), X‐ray fluorescence (XRF), and inductively coupled plasma mass spectrometry (ICP‐MS). In addition, theoretical calculations of the entropies and energies of formation of activated complexes of the hydrogenation reactions of 1‐hexyne and 1‐hexene in the gas phase have been calculated with Gaussian 09 software using the density functional theory (DFT) B3LYP/cc‐pVQZ method. It was found that the presence of dysprosium in the structure of mesoporous silica gel leads to an increase in catalytic activity in the hydrogenation of 1‐hexyne. Moreover, it was shown that mesoporous silica gel modified with copper has the highest selectivity for hexene‐1 in the hydrogenation reaction of 1‐hexyne/1‐hexene mixture at 130°C.
... [1][2][3][4][5][6][7][8][9][10][11][12][13] It has been widely studied and utilized in various techniques for functional group interconversions. [14][15][16][17] Difunctionalization of alkenes is an attractive method for introducing a set of groups during a 2 one-pot reaction process. [18][19] Dithiocyanation of alkynes and alkenes is meaningful as they shows fungicidal activity. ...
A transition metal-free process has been reported for 1,2-dithiocyanation of alkynes in the presence of sodium persulfate and potassium thiocyanate reagent combination in a short reaction time under ambient air. Styrene derivatives are equally applicable under the same reaction conditions. Monothiocyanated vinyl derivatives were also synthesized from 2-ethynylpyridine and dimethyl acetylene dicarboxylate. The reaction proceeds by the radical/polar pathway as evidenced from our experiments and literature. After removal of the solvent from the reaction mixture by evaporation, the crude product was purified without conventional workup.
A copper-catalyzed aminocyanation of alkenes has been achieved through distal cyano migration using O-benzoylhydroxylamines and N-fluorobenzenesulfonimides. This method offers a rapid approach to generate diverse β-amino and β-sulfonimido nitriles. These reactions feature mild conditions, tolerance of sensitive functional groups, and excellent regioselectivity. Mechanistic studies suggest that these transformations are initiated by a copper-catalyzed amination step followed by a cyano migration step.
A three-component reaction for 1,2-amino oxygenation of 1,3-dienes has been achieved using O-acyl hydroxylamines and carboxylic acids. The reaction occurs through copper-catalyzed amination of olefins followed by nucleophilic addition of carboxylic acids, offering high levels of chemo-, regio-, and site-selectivity. The method is effective for both terminal and internal 1,3-dienes, including those bearing multiple, unsymmetrical substituents. The amino oxygenation conditions also exhibited remarkable selectivity toward 1,3-dienes over alkenes, good tolerance of sensitive functional groups, and reliable scalability.
Electroorganic synthesis is an emerging area of high impact research in organic chemistry, which is considered as one of the green and efficient methods and attracts growing research attention. In this review, we summarized comprehensively the recent literature reports on the electrochemical oxidative difunctionalization of unsaturated C—C bonds. The reaction types described in this review included electrochemical intermolecular cyclization, electrochemical intramolecular cyclization, and electrochemical difunctionalization of alkenes/alkynes. This review focuses on the discussion of its synthetic generality for the preparation of functionalized compounds and the related electrochemical oxidative reaction mechanism.
An efficient electrochemical approach to the vicinal iodoazides has been developed through constant current electrolysis of alkenes with NaN3 and NaI in methanol. The reaction is proposed to proceed via a cyclic iodonium intermediate and thereby gives Markovnikov addition products exclusively.
A visible light-mediated photocatalytic bis(alkoxycarbonyl)methylation/ring expansion of alkenyl cyclobutanols is described. This approach provides a mild and operationally simple access to the synthesis of bis(alkoxycarbonyl)methyl-substituted cyclic ketones from the coupling reaction of 1-(1-arylvinyl)cyclobutanols with aryl bromomalonates.
Copper (Cu) species show versatile chemical reactivity enabling functionalization of rather simple molecules in a variety of the reaction modes. The research on development of Cu-catalyzed oxidative molecular transformation has now a momentum in the community of synthetic organic chemistry, resulting in discovery of many kinds of molecular transformations for synthesis of complex molecules of medicinal and materials importance. To make catalytic turnover in Cu-catalyzed oxidative processes, use of stoichiometric oxidants is indispensable. These stoichiometric oxidants could uniquely change the reaction mechanism in the catalytic cycle to result in different outcomes (i.e., structure of the products and selectivity) from the same kinds of starting materials. This digest focuses on the role of the stoichiometric oxidants in several copper catalyzed oxidative molecular transformations of amidine derivatives (reported since 2008) primarily for the synthesis of nitrogen heterocycles.
A cascade radical oxidative difunctionalization of alkynoates with simple ethers for the construction of tri-substituted olefins is developed. The reaction undergoes cascade radical addition to C-C triple bond, 1,4-aryl migration, and decarboxylation to deliver a variety of difunctionalized alkenes in moderate to good yields. This procedure also represents a promising strategy for the direct functionalization of the α-Csp3-H bonds in ether derivatives.
Iron-catalyzed alkoxycarbonylation–peroxidation of alkenes with carbazates and T-Hydro was developed. A variety of β-ester peroxides were synthesized efficiently and selectively in a single step starting from readily available starting materials.
