Recyclable Enantioselective Catalysts Based on Copper(II) Complexes of 2‐(Pyridine‐2‐yl)imidazolidine‐4‐thione: Their Application in Asymmetric Henry Reactions

This paper describes the preparation of enantioselective catalysts based on derivatives of imidazolidine‐4‐thione and their subsequent anchoring by means of a sulfur atom on a polymeric carrier. First, we verified the catalytic activity and enantioselectivity in the Henry reaction of the homogeneous variants of the catalysts, i.e., the copper(II) complexes of 2‐(pyridine‐2‐yl)imidazolidine‐4‐thiones and 4‐benzylsufanyl‐2‐(pyridine‐2‐yl)imidazolines themselves. It was found that these catalysts exhibit high enantioselectivity (up to 98% ee). Subsequently, the imidazolidine‐4‐thione catalysts were immobilized by anchoring to polymeric carriers based on a copolymer of styrene and 4‐vinylbenzyl chloride. These heterogeneous catalysts were analogously tested with regard to their catalytic activity and enantioselectivity in the Henry reaction, and moreover, the possibility of their separation and reuse was studied. It was found that all the prepared immobilized catalysts are highly enantioselective (up to 97% ee). Their recycling ability was tested in Henry reaction of 2‐methoxybenzaldehyde with nitromethane. It was found that they can be recycled more than ten times without any decrease of their enantioselectivity. Therefore, they present a better means of catalysis than the original copper(II) complexes of imidazolidine‐4‐ones from both economic as well as ecological points of view. Thus, such immobilized catalysts exhibit high application potential for the asymmetric Henry reaction.

     

Supported Gold Nanoparticles‐Catalyzed Microwave‐Assisted Hydration of Nitriles to Amides under Base‐Free Conditions

Polystyrene‐supported gold (Au@PS) nanoparticles were synthesized by the reduction deposition approach and well characterized by UV‐visible, XRD, TEM, SAED, EDX, and XPS studies. The Au@PS was applied as catalyst for the hydration of nitriles to amides in water under microwave irradiation. Several functionalized aromatic, heterocyclic and aliphatic nitriles were found to be active for synthesis of the corresponding amides where no activation of water by base, ligand and support is needed. Easy recovery, negligible leaching and recyclability for up to eight runs are added advantages of the catalyst under water‐mediated reaction conditions.

     

Prolinamides versus Prolinethioamides as Recyclable Catalysts in the Enantioselective Solvent‐Free Inter‐ and Intramolecular Aldol Reactions

A solvent‐free asymmetric and direct anti‐aldol reaction of aliphatic ketones with aromatic aldehydes catalyzed by recyclable L ‐prolineamides and L ‐prolinethioamides 3 is studied. The L ‐prolinethioamide 3d (5 mol%), derived from L ‐Pro and (R)‐1‐aminoindane, is the most efficient catalyst for this process affording the anti‐aldol adducts in high yields with excellent diastereo‐ and enantioselectivities (up to >98/2 dr, up to 98% ee) at 0 °C or room temperature. Prolinethioamide 3d is an effective organocatalyst for the first asymmetric, solvent‐free, intramolecular Hajos–Parrish–Eder–Sauer–Wiechert reaction with comparable or higher levels of enantioselectivity (up to 88% ee) to reported catalysts in organic solvents. Moreover, organocatalyst 3d can be easily recovered and reused by a simple acid/base extraction.     

Immobilization of MacMillan Imidazolidinone as Mac‐SILC and its Catalytic Performance on Sustainable Enantioselective Diels–Alder Cycloaddition

MacMillan’s imidazolidinone catalyst was immobilized as a supported ionic liquid catalyst (Mac‐SILC) in the pores of silica gel with the aid of an ionic liquid – 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide. The heterogenized organocatalyst was utilized for the enantioselective Diels–Alder reaction of cyclopentadiene and cinnamaldehyde, recovered by simple filtration and subsequent evacuation, and repeatedly used up to six times in 81% average chemical yield, 87% ee for endo‐ and 80% ee for exo‐products. The Mac‐SILC was effective for a variety of substrates.     

Grafting of Molecularly Ordered Mesoporous Phenylene‐Silica with Molybdenum Carbonyl Complexes: Efficient Heterogeneous Catalysts for the Epoxidation of Olefins

Arenetricarbonyl complexes, or the general formula  C₆H₄Mo(CO)₃ , were incorporated into crystal‐like mesoporous phenylene‐silica by liquid‐phase deposition of molybdenum hexacarbonyl [Mo(CO)₆]. By adjusting the reaction conditions, different molybdenum loadings of 1.5 and 5.9 wt% were obtained, which correspond to 3% and 14% of the phenylene contents. The texture properties of the materials as well as the nature of the surface‐fixed complexes were characterized by powder X‐ray diffraction, transmission electron microscopy (TEM), N₂ adsorption, FT‐IR, UV‐vis and MAS (¹³C, ²⁹Si) NMR spectroscopy. The derivatized organosilicas were examined as catalyst precursors for the liquid‐phase epoxidation of cis‐cyclooctene, 1‐octene, trans‐2‐octene and (R)‐(+)‐limonene at 55 °C, using tert‐butyl hydroperoxide as the oxidant. For each olefin the corresponding epoxide was the only product detected. In the case of cyclooctene, the intrinsic reaction rates per surface molybdenum atom were similar for both Mo loadings (TOF∼1150 mol mol_Mo⁻¹ h⁻¹), suggesting that the resultant materials act as single site epoxidation catalysts. Leaching tests and metal analyses of reaction solutions showed that the catalytic activity stemmed from the immobilized species and not from the leaching of active species into solution. The oxidation of limonene gave limonene oxide as the only product in 95% yield at 3 h, which reveals an outstanding regioselectivity to the epoxidation of the endocyclic double bond.     

Solvent‐Free Aerobic Oxidation of Alcohols Catalyzed by an Efficient and Recyclable Palladium Heterogeneous Catalyst

A simple alumina‐supported palladium catalyst prepared by an adsorption method is highly efficient and recyclable in the solvent‐free oxidation of alcohols with molecular oxygen. The adsorption method results in high dispersion of palladium probably as mononuclear or oligonuclear species on alumina surface. These palladium species are transformed to small Pd nanoparticles (ca. 5 nm), which are probably the true active species, during the course of alcohol oxidation.     

An Efficient Tetrabutylammonium Fluoride (TBAF)‐Catalyzed Three‐Component Synthesis of 3‐Substituted Indole Derivatives under Solvent‐Free Conditions

An expedient and efficient one‐pot three‐component synthesis of 3‐substituted indoles has been developed by the reaction of indoles, active methylene compounds and aldehydes using a catalytic amount of tetrabutylammonium fluoride under solvent‐free conditions.     

Encapsulated Cobalt Oxide on Carbon Nanotube Support as Catalyst for Selective Continuous Hydrogenation of the Showcase Substrate 1‐Iodo‐4‐nitrobenzene

A carbon nanotube supported catalyst containing cobalt/cobalt oxide (Co/Co₃O₄) nanoparticles encapsulated within a shell of nitrogen‐doped graphene layers (Co₃O₄/NGr@CNT) was prepared. It shows excellent chemoselectivity in the hydrogenation of 1‐iodo‐4‐nitrobenzene, which contains an iodine substituent highly sensitive against hydrodehalogenation. In contrast to traditional activated charcoal‐supported catalysts such as Pt‐V/C or the closely related Vulcan carbon black supported Co₃O₄/NGr@C, the advantageous morphological properties of the CNT support allow for the application of the new Co₃O₄/NGr@CNT as a fixed bed catalyst in a continuous flow reactor. Under optimized conditions, no dehalogenation side products could be detected. This remarkable selectivity in combination with its mechanical stability under operation conditions render Co₃O₄/NGr@CNT a catalyst particularly relevant for application in continuous processes based on a packed bed reactor.

     

Effect of the Helical Tether of a Resin‐Supported Peptide Catalyst for Friedel–Crafts‐Type Alkylation in Water

A detailed investigation of the helical part of the resin‐supported peptide catalyst possessing a turn motif and helical unit was conducted to clarify the structure‐activity relationship. The peptide catalyst with an α‐ or 3₁₀‐helical tether was effective for an enantioselective Friedel–Crafts‐type alkylation in water. From the spectral analysis of the peptide with an optimum sequence, it was demonstrated that the helical moiety of the peptide catalyst played a role for stabilizing a terminal turn structure.     

Recent advances in the production of γ‐valerolactone from biomass‐derived feedstocks via heterogeneous catalytic transfer hydrogenation

γ‐valerolactone (GVL) is an important intermediate chemical with a wide range of applications as fuel, fuel additive and as a green solvent which has received a great deal of attentions from both academia and industry. This review aims to summarise the advances in conversion of renewable feedstocks into GVL through heterogeneous catalytic transfer hydrogenation (CTH) with a strong emphasis on discussing preparation, characterisation and performance of the catalysts in order to provide a better understanding of various catalytic systems and also to compare them in terms of catalytic performance. © 2017 Society of Chemical Industry     

Taking “Nothing” into Consideration: Supported Metal Catalysts by SAXS

The analysis of the X‐ray diffraction patterns scattered at small‐angles (SAXS) by porous materials is a powerful analytical tool providing relevant structural information on supported metals used as heterogeneous catalysts. In particular, the technique offers valuable structural insights on the interphases which govern the chemical behaviour of these materials. Using a series of silica‐supported palladium catalysts we show how SAXS experiments address the crucial importance of porosity (or “nothing”) in affecting the structure of these catalysts.     

Poly(styrene) Resin‐Supported Cobalt(III) Salen Cyclic Oligomers as Active Heterogeneous HKR Catalysts

A cross‐linked poly(styrene) support functionalized with cobalt(III) salen cyclic oligomers that can be used as a catalyst for the hydrolytic kinetic resolution (HKR) of terminal epoxides is reported. This catalyst is the most active heterogeneous catalyst to date for the HKR of terminal epoxides and can be recycled more than six times with excellent enantioselectivities for the HKR of epichlorohydrin. A 3‐fold rate enhancement was observed when conducting the HKR reaction with 6 equivalents of water compared to 0.6 equivalents. We hypothesize that this rate enhancement is due to water sequestration of the diol product from the organic phase, thereby maintaining a high local concentration of epoxides and catalyst in the organic phase.     

Semiconductor‐Gold Nanocomposite Catalysts for the Efficient Three‐Component Coupling of Aldehyde,Amine and Alkyne in Water

An efficient heterogeneous lead sulfide‐gold catalyst has been successfully developed for the synthesis of propargylic amines via a three‐component coupling reaction of aldehyde, amine and alkyne in water. The process is simple and applicable to a diverse range of aromatic and aliphatic aldehydes, amines and alkynes. Furthermore, the catalyst is stable to air and water, and can be easily recovered and reused.     

Enantioselective Alcoholysis of meso‐Glutaric Anhydrides Catalyzed by Cinchona‐Based Sulfonamide Catalysts

The bifunctional Cinchona‐based sulfonamide catalysts showed the highest levels of enantioselectivity reported to date in the alcoholytic desymmetrization of meso‐glutaric anhydrides. Density functional theory (DFT) computational studies provide detailed insight into the observed sense of enantioselectivity. Moreover, detailed experimental studies and single crystal X‐ray analysis confirmed that these bifunctional organocatalysts 3 do not form H‐bonded self‐aggregates in both solution and solid state. The synthetic utility of this methodology was also demonstrated in the synthesis of pharmaceutically important γ‐amino acids, such as (S)‐pregabalin. Of the many asymmetric syntheses of enantiomerically pure (S)‐pregabalin reported to date, our synthesis requires the least number of and the simplest steps.     

A New Class of Heterogeneous Platinum Catalysts for the Chemoselective Hydrogenation of Nitroarenes

A new series of nanostructured platinum catalysts able to catalyze the selective reduction of nitroarenes has been developed. The materials, made of organosilica physically doped with nanostructured platinum(0), are stable and efficient. Reactions in general proceed with high yield and often go to completion, while the catalysts can be reused in further reaction runs. This establishes a new class of relevant solid catalysts for synthetic organic chemistry named SiliaCat Platinum‐Hydrogel.     

First Heterogeneous Ligand‐ and Salt‐Free Larock Indole Synthesis

A new ligand‐ and salt‐free procedure using heterogeneous palladium catalysts for the Larock indole and benzofuran synthesis is reported. After optimisation of the reaction conditions, good to high isolated yields have been achieved for a variety of structures. Recycling studies have shown that the palladium catalysts can be readily recovered and reused. Reactions and recovery of the palladium catalysts can be carried out in the presence of air, without any particular precaution.     

Sol‐Gel Ormosils Doped with TEMPO as Recyclable Catalysts for the Selective Oxidation of Alcohols

Organically modified silicas doped with TEMPO prepared via the sol‐gel method are highly recyclable catalysts of the selective Montanari‐Anelli oxidation of 1‐nonanol; They show a notable ”positive feedback” effect of matrix alkylation on the catalyst activity which is typical of doped sol‐gel materials and markedly differentiates the behaviour of these materials from that of analogous silica‐supported TEMPO.     

Robust Silver(I) Catalyst for the Carboxylative Cyclization of Propargylic Alcohols with Carbon Dioxide under Ambient Conditions

Inspired by the bulkier bis(triphenylphosphine)–silver cation‐induced mechanism of propargylic alcohols and carbon dioxide through the alkyl carbonate intermediate, a robust dual‐component catalytic system consisting of silver acetate and tetraheptylammonium bromide was rationally developed for the synthesis of α‐methylene cyclic carbonates under ambient conditions without employing any additional organic base and ligand. This is one of the most effective catalysts reported to date for this conversion, with a very high turnover number of up to 6024, probably due to the synergistic effect of Lewis basic and Lewis acidic species for the activation of both propargylic alcohol and carbon dioxide by the formation of the alkyl carbonate with a bulkier counterion. Notably, this catalyst also worked well for the carboxylative cyclization of propargylic amines with carbon dioxide with the highest turnover number of 544.