The mechanism-oriented reaction design for the divergent synthesis of chiral molecules from simple starting materials is highly desirable. In this work, aromatic amide-derived nonbiarylatropisomer/silver (silver/Xing-Phos) complex was used to catalyze the Michael addition of glycine aldimino esters to chalcones and successfully applied to the subsequent cyclocondensation to afford substituted cis-Δ(1)-pyrroline derivatives with up to 98 % ee. Besides the inherent performance of the chiral Ag/Xing-Phos catalyst system, it was found that the workup of such reactions played an important role for the stereoselective construction of stereodivergent Δ(1)-pyrrolines, in which an epimerization of the cis-Δ(1)-pyrrolines to the trans-isomers during was revealed.

A ferrocene-based ionic liquid (Fe-IL) is used as a metal-containing feedstock with a nitrogen-enriched ionic liquid (N-IL) as a compatible nitrogen content modulator to prepare a novel type of non-precious-metal–nitrogen–carbon (M-N-C) catalysts, which feature ordered mesoporous structure consisting of uniform iron oxide nanoparticles embedded into N-enriched carbons. The catalyst Fe¹⁰@NOMC exhibits comparable catalytic activity but superior long-term stability to 20 wt % Pt/C for ORR with four-electron transfer pathway under alkaline conditions. Such outstanding catalytic performance is ascribed to the populated Fe (Fe₃O₄) and N (N2) active sites with synergetic chemical coupling as well as the ordered mesoporous structure and high surface area endowed by both the versatile precursors and the synthetic strategy, which also open new avenues for the development of M-N-C catalytic materials.

A series of palladium–NHC compounds were prepared and their catalytic activity in the double carbonylation of aryl iodides to synthesize α-keto amides were examined. Palladium complexes bearing mixed NHC–phosphine exhibited high efficiency for the double carbonylation reaction. The effects of different solvents, base, temperature, carbon monoxide (CO), pressure, various amine and aryl iodides were investigated. Both electron-rich and electron-deficient aryl iodides afforded the corresponding substituted α-keto amides in moderate to good yields. A possible mechanism was also proposed. Copyright © 2013 John Wiley & Sons, Ltd.

Remote stereocontrol through conformational transmission along a carbon chain is highly important in synthetic systems and molecular architectures. In this work, the interactional reactivity between a remote silicon-based bulky group and an O-/N-containing functional group has been revealed and determined by lateral lithiation–substitution, desilylation, as well as desilylation–olefination with benzaldehyde. The results suggest considerable information transmission and steric hindrance that can be exploited for the controllable synthesis of atropisomeric molecules. Based on the remote steric effect of a functional group across the aromatic ring of an amide, the construction of isolable atropisomeric amides with functional groups, such as alcohol, amine, and olefin was successfully achieved. All these new atropisomers were obtained in reasonable yield in pure diastereomeric form, and the specific configuration of representative products was confirmed by X-ray crystallography.

Nitrogen-functionalized active carbon-supported ultrasmall Pd nanoparticles were conveniently prepared by using a postloading method. The Pd catalyst was highly active and selective for the hydrogenation of nitroarenes at room temperature under ambient pressure. Reducible groups such as ketone, carboxylic acid, and ester were not hydrogenated, and the corresponding anilines were obtained quantitatively. The Pd catalyst demonstrated high stability and could be reused 10 times without the loss of catalytic performance.

A series of sulfonic acid-functionalized (SO₃H-functionalized) ionic liquids was synthesized and used as metal-free, highly selective and efficient catalysts for the direct amination of alcohols. Notably, the activities of the series of SO₃H-functionalized ionic liquids were compared and a 92% isolated yield was obtained using 3-tetradecyl-1-(butyl-4- sulfonyl)imidazolium trifluoromethanesulfonate ([BsTdIM][OTf]) as the catalyst. Importantly, the catalytic system has wide substrate scope including benzylic, allyl, propargylic, aliphatic alcohols with sulfonamide, amide, carbamate, aromatic amine and N-heterocyclic compounds. Interestingly, the system was also suitable for a multi-gram scale direct amination of alcohols. Additionally, the reusable nature of [BsTdIM][OTf] makes this protocol more attractive and avoids the disposal and neutralization of acidic catalysts. Moreover, preliminary experiments indicated that this reaction should proceed via an S_N1 pathway.

The direct CH benzylation of azoles with benzyl chlorides proceeds efficiently, via sequential cleavage of one sp² CH bond and two sp³ CH bonds in the presence of a palladium catalyst, to generate a wide range of tribenzylated azoles with a quaternary carbon center efficiently. The same catalyst could also promote the mono- and di-benzylation reactions through fine turning of the base and reaction conditions.

Cross-linked polymeric ionic liquid material-supported copper (Cu-CPSIL), imidazolium-loaded Merrifield resin-supported copper (Cu-PSIL) and silica dispersed CuO (CuO/SiO₂), were prepared and proved to be efficient catalysts for the one-pot synthesis of 1,4-disubsituted-1,2,3-triazoles by the reaction of alkyl halides with sodium azide and terminal alkynes in water at room temperature. Moreover, these supported copper catalysts were recovered quantitatively from the reaction mixture by simple filtration and reused for five consecutive recycles without significant loss of catalytic activity. Among the three immobilized copper catalysts, Cu-CPSIL exhibited excellent catalytic activity for the reaction of aliphatic bromides, sodium azide and terminal alkynes. The differences in the catalytic performances of the catalysts could be ascribed to the copper dispersion and the interaction between copper and the supports. In addition, water was used as the reaction media and the proton provider, the latter was found to be very important for the reaction. The XPS results suggested that the supported Cu(II) catalysts were reduced to catalytic Cu(I) species via alkynes homocoupling reaction. By means of IR and ESI-MS studies, a possible mechanism of cycloaddition based on the reduction of Cu(II) to Cu(I) species was proposed.

A highly efficient and eco-friendly esterification was achieved by a series of novel dicationic acidic ionic liquids (DAILs) containing double SO₃H cations. High yields of the product esters were obtained by using 2 mol% of the DAILs as catalysts and DAIL I could be reused at least ten times without appreciable loss of its efficicency.