Diarylprolinol in an asymmetric aldol reaction of an α-alkyl-α-oxo aldehyde as an electrophile

The direct aldol reaction of an α-alkyl-α-oxo aldehyde was catalyzed by trifluoromethyl-substituted diarylprolinol 1 to afford a γ-oxo-β-hydroxy-α-substituted aldehyde in good yield with excellent anti-selectivity and excellent enantioselectivity.     

Solid supported Hayashi–Jørgensen catalyst as an efficient and recyclable organocatalyst for asymmetric Michael addition reactions

A comparison of three different catalytic systems for the efficient, asymmetric synthesis of N-({(3R,4R)-4-[(benzyloxy)methyl]pyrrolidin-3-yl}methyl)-N-(2-methylpropyl)benzenesulfonamide 1 (BZN) is described. The presented strategy is based on the organocatalytic Michael addition of aldehyde 2 to trans-nitroalkene 3, and subsequent reductive cyclization. High yields, enantio-, and diastereoselectivities were achieved in the Michael addition by application of a POSS- or Wang resin-supported Hayashi–Jørgensen catalyst.     

First asymmetric nucleophilic displacement reactions on chiral α-substituted aldehyde hydrazones

The first asymmetric nucleophilic substitution reaction on racemic α-substituted aldehydes using enantiomerically pure hydrazines as chiral auxiliaries is presented. The diastereoselectivity of the process is achieved by a dynamic kinetic resolution via the 1:1 epimeric mixture of the substrate hydrazones. The a²-reactivity (Umpolung) of the α-substituted hydrazones is accomplished by complexation with Lewis acids. Several carbon-, sulfur- and oxygen-nucleophiles were shown to readily undergo substitution of the α-leaving group under these conditions, affording the substitution products with good to excellent chemical yields and with low to moderate diastereoselectivities. Two methods for the cleavage of the chiral auxiliary are described.     

α-Pinene-type chiral Schiff bases as tridentate ligands in asymmetric addition reactions

A group of tridentate Schiff bases derived from (+)-α-pinene were synthesized. The steric effects in the transition state, the importance of π-π stacking interactions as well as the electronic effects of aryl aldehydes according to Hammett constant values in the enantioselective addition of Et₂Zn to aldehydes with the use of Schiff bases as chiral ligands are described. Also, a variety of aldehydes were cyanated using a catalyst prepared in situ from titanium tetraisopropoxide and chiral Schiff bases. The influence of a conjugated double-bond in the cyanation substrates on enantioselectivity was observed. The chemical structures of the chiral Schiff base-titanium alkoxide complexes are discussed based on their ¹H and ¹³C NMR spectra. 3D models of the Zn₂-complex catalyst and Ti-complex catalyst containing α-pinane-type Schiff bases based on X-ray diffraction experiments are postulated. The models presented were consistent with the reported chirality of the addition product and observed ee.     

An efficient asymmetric aldol reaction of Chan's diene promoted by chiral Ti(IV)–BINOL complex

1,3-Bis-(trimethylsilyloxy)-1-methoxy-buta-1,3-diene (Chan's diene) can be conveniently used in asymmetric aldol reaction with aromatic, heteroaromatic, α,β-unsaturated and aliphatic aldehydes in the presence of catalytic amounts (2–8% mol) of chiral Ti(IV)/(R)-BINOL complex.     

Palladium-catalyzed asymmetric Diels–Alder reactions with novel chiral imino-phosphine ligands

Palladium-catalyzed asymmetric Diels–Alder reactions have been achieved with considerably high enantioselectivity by using chiral imino-phosphine ligands derived from (1S,4R)-(+)-fenchone, (1R,2R,5R)-(+)-2-hydroxy-3-pinanone derivatives, (1S,5R)-(−)-menthone, (1R,4R)-(+)-camphor, and (1S)-(+)-ketopinic acid. A mechanism for the asymmetric induction is proposed on the basis of the stereochemical outcome of the reactions.     

Direct asymmetric aldol reactions in brine with recyclable fluorous β-aminosulfonamide organocatalysts

Fluorous organocatalyst 3 promotes direct asymmetric aldol reactions of ketones with aldehydes in brine, leading to the synthesis of the corresponding anti-aldol products in high yields with up to 96% ee. Fluorous organocatalyst 3 is easily recovered by solid-phase extraction using fluorous silica gel and can be reused up to five times without purification.     

Palladium tetrazole–supported complex as an efficient catalyst for the Heck reaction

Abstract  

A tetrazole-supported polymeric ligand has been synthesized. The palladium complex derived from the polymeric material has been evaluated as a catalyst for the Heck reaction of aryl iodides and bromides with styrene to provide the corresponding products in high yields. The reaction proceeded smoothly in the presence of 1 mol% with respect to Pd of catalyst in DMF at 125 or 140 °C within 1–3 h. Recycling studies showed that the catalyst can be readily recovered and reused for several times without significant loss of catalytic activity.     

Studies directed towards anthracyclinone syntheses: The use of d-glucose as a chiral auxiliary in asymmetric Diels–Alder reactions

Setting up the correct functionality with the correct stereochemistry in the ring-A of anthracycline precursors represents a synthetic challenge. The use of d-glucose as a chiral auxiliary either on the silyloxy diene or naphthoquinone-based dienophile to form the ring-A using asymmetric Diels–Alder reactions as developed by the Stoodley group and is the focus of this review. The endo-transition state is described based on a frontier orbital approach and the HOMO–LUMO energy gaps were estimated using semi-empirical (MNDO) calculations with SPARTAN’08. As anthracyclines are used in chemotherapy, some of their associated biochemistry and clinical effectiveness are also briefly introduced.     

α-Hydroxy ketones as useful templates in asymmetric reactions

Approaching the Nature's efficiency in controlling both reactivity and stereoselectivity of organic reactions by means of a catalyst species remains a formidable challenge for chemists to face. Despite impressive advances in the design of novel catalysts and activation modes, current catalytic and asymmetric methodologies rarely meet desirable standards of robustness, substrate scope, and selectivity altogether. One trick to improve catalyst behaviour is to identify adequate substrate template-catalyst combinations so that optimum performance of the reaction system could be achieved. During the last couple of years α-hydroxy ketones, and most particularly α'-hydroxy enones, have emerged as useful templates with applications in a number of metal-catalyzed as well as organocatalyzed C-C and C-X bond-forming stereoselective reactions. The first review of these accomplishments is presented here along with a brief historical introduction.     

Lewis acid mediated asymmetric Diels–Alder reactions of chiral 2-phosphonoacrylates

2-Phosphonoacrylates containing four chiral alcohol auxiliaries were efficiently prepared and evaluated in Lewis acid mediated Diels–Alder reactions. Under the activation of SnCl₄, all reactions performed in CH₂Cl₂ at ?65 °C exclusively afforded the endo (endo-to-carboxylate) cycloadducts with dr’s ranging from 50:50 to >99:1. The best facial selectivity was obtained from the substrate bearing a (?)-phenylmenthyl group, to give adducts as (dr >99:1) or almost as (dr = 99:1) single diastereomers. Detailed strategies for the structural elucidation of the cycloadducts as well as a rationalization of the observed stereoselectivity are described.     

Study of asymmetric aldol and Mannich reactions catalyzed by proline–thiourea host–guest complexes in nonpolar solvents

A proline–thiourea host–guest complex has been described as a good catalyst for asymmetric reactions such as aldol and Mannich reactions. High stereoselectivities were obtained under optimal conditions. Thiourea was observed to have an important effect on the reactivity and selectivity, even in an unconventional nonpolar reaction medium and without the need to utilize low temperatures. This proline–thiourea host–guest system has the ability to participate in a hydrogen bonding network.     

Cu(OAc)2 entrapped on ethylene glycol-modified melamine–formaldehyde polymer as an efficient heterogeneous catalyst for Suzuki–Miyaura coupling reactions

Research on Chemical Intermediates - This work is described as an environmental friendly approach for Cu(OAc)2 entrapped on ethylene glycol-modified melamine–formaldehyde-based polymeric...     

Bimetallic Cu–Pt/nanoporous carbon composite as an efficient catalyst for methanol oxidation

A novel bimetallic Cu–Pt nanoparticle supported onto Cu/indirectly carbonized nanoporous carbon composite (Cu–Pt/ICNPCC) was prepared through a two-step process: first, carbonization of furfuryl alcohol-infiltrated MOF-199 [metal–organic framework Cu₃(BTC)₂ (BTC?=?1,3,5-benzene tricarboxylate)], without removing the Cu metal with HF aqueous solution; second, the partial galvanic replacement reaction (GRR) of Cu nanoparticles by Pt^IV upon immersion in a platinum(IV) chloride solution. The synthesized materials characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDS), and electrochemical methods. The EDS result revealed that part of Cu nanoparticles have been substituted by Pt nanoparticles after GRR. The methanol oxidation at the surface of Cu–Pt/ICNPCC was investigated by cyclic voltammetry method in 0.5 M H₂SO₄ and indicated good electro-catalytic activity towards methanol oxidation (E_p?=?0.85 V vs. NHE and j_f?=?1.00 mA cm^?2). It is suggested that this improvement is attributed to the effect of proper Cu/ICNPCC for fine dispersion, efficient adhesion, and prevention of Pt coalescing.     

Hollow cobalt oxide nanoparticles embedded in nitrogen-doped carbon nanosheets as an efficient bifunctional catalyst for Zn–air battery

Rational design of low-cost, highly electrocatalytic activity, and stable bifunctional electrocatalysts for oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) has been a great significant for metal–air batteries. Herein, an efficient bifunctional electrocatalyst based on hollow cobalt oxide nanoparticles embedded in nitrogen-doped carbon nanosheets(Co/N-Pg) is fabricated for Zn–air batteries. A lowcost biomass peach gum, consisting of carbon, oxygen, and hydrogen without other heteroatoms, was used as carbon source to form carbon matrix hosting hollow cobalt oxide nanoparticles. Meanwhile, the melamine was applied as nitrogen source and template precursor, which can convert to carbon-based template graphitic carbon nitride by polycondensation process. Owing to the unique structure and synergistic effect between hollow cobalt oxide nanoparticles and Co-N-C species, the proposal Co/N-Pg catalyst displays not only prominent bifunctional electrocatalytic activities for ORR and OER, but also excellent durability. Remarkably, the assembled Zn–air battery with Co/N-Pg air electrode exhibited a low discharge-charge voltage gap(0.81 V at 50 mA cm~(-2)) and high peak power density(119 mW cm~(-2)) with long-term cycling stability. This work presents an effective approach for engineering transition metal oxides and nitrogen modified carbon nanosheets to boost the performance of bifunctional electrocatalysts for Zn–air battery.     

Synthesis of thiazole derivatives using magnetic nano zirconia–sulfuric acid as an efficient and recyclable catalyst in water

Russian Journal of General Chemistry - Fe3O4 magnetic core covered by zirconia shell bearing sulfonic acid groups (Fe3O4@ZrO2–SO3H) was prepared and used as an efficient acidic catalyst in...