Chiral synthesis on catalysts immobilized in microporous and mesoporous materials

This paper reviews the recent progress made in the asymmetric synthesis on chiral catalysts in porous materials and discusses the effects of surface and pores on enantio-selectivity (confinement effect). This paper also summarizes various approaches of immobilization of the chiral catalysts onto surfaces and into pores of solid inorganic supports such as microporous and mesoporous materials. The most important reactions surveyed for the chiral synthesis in porous materials include epoxidation. hydrogenation, hydroformylation, Aldol and Diels-Alder reactions, etc. The confinement effect originated from the surfaces and the pores turns out to be a general phenomenon. which may make the enantioselectivity increase (positive effect) or decrease (negative effect). The confinement effect becomes more pronounced particularly when the bonding between the catalyst and the surface is more rigid and the pore size is tuned to a suitable range. It is proposed that the confinement in chiral synthesis is essentially a consequence of subtle change in transition states induced by weak-interaction in pores or on surfaces. It is also anticipated that the enantioselectivity could be improved by tuning the confinement effect based on the molecular designing of the pore/surface and the immobilized catalysts according to the requirements of chiral reactions.

Synthesis of novel ferrocenylphosphine-amidine ligands with central and planar chirality and their diastereomeric effect in Pd-catalyzed asymmetric allylic alkylation

Some novel ferrocenylphosphine-amidine ligands with central and planar chirality were prepared from (R,S-p)-PPFNH2-R 3 and its diastereomer (S,S-p)-PPFNH2 3a. The efficiency and diastereomeric impact of these ferrocenylphosphine-amidine ligands in the palladium-catalyzed asymmetric allylic substitution was examined, and up to 96% e.e. with 98% yield was achieved by the use of ligand (R,S-p)-4a with a methyl group in the amidino moiety. The results also indicated that (R)-central chirality and (S-p)-planar chirality in these ferrocenylphosphine-amidine ligands were matched for the palladium-catalyzed asymmetric allylic alkylation. (C) 2003 Elsevier Ltd. All rights reserved.

Structural probing of D-fructose derived ligands for asymmetric addition of diethylzinc to aldehydes

A series of new chiral ligands derived from D-fructose have been synthesized and applied in the enantioselective addition of diethylzinc to aldehydes. Comparison of the enantioselectivities obtained with these ligands demonstrated that the catalytic properties are highly dependent upon the structure of ligands, a rational explanation of the structural effects on the catalytic properties is provided. (C) 2003 Elsevier Science Ltd. All rights reserved.

In situ IR spectroscopic studies on molybdenum nitride catalysts: active sites and surface reactions

Recent IR spectroscopic studies on the surface properties of fresh Mo2N/gamma-Al2O3 catalyst are presented in this paper. The surface sites of fresh Mo2N/gamma-Al2O3, both Modelta+ (0<δ<2) and N sites, are probed by CO adsorption. Two characteristic IR bands were observed at 2045 and 2200 cm(-1), due to linearly adsorbed CO on Mo and N sites, respectively. The surface N sites are highly reactive and can react with adsorbed CO to form NCO species. Unlike adsorbed CO on reduced passivated one, the adsorbed CO on fresh Mo2N/gamma-Al2O3 behaves similarly to that of group VIII metals, suggesting that fresh nitride resembles noble metals. It is found that the surface of Mo nitrides slowly transformed into sulfide under hydrotreating conditions, which could be the main reason for the activity drop of molybdenum nitride catalysts in the presence of sulfur-containing species. Some surface reactions, such as selective hydrogenation of 1,3-butadiene, isomerization of 1-butene, and hydrodesulfurization of thiophene, were studied on both fresh and reduced passivated Mo2N/gammaAl(2)O(3) catalysts using IR spectroscopy. The mechanisms of these reactions are proposed. The adsorption and reaction behaviors of these molecules on fresh molybdenum nitride also resemble those on noble metals, manifesting the unique properties of fresh molybdenum nitride catalysts. Mo and N sites are found to play different roles in the adsorption and catalytic reactions on the fresh Mo2N/gammaAl(2)O(3) catalyst. Generally, Mo sites are the main active sites for the adsorption and reactions of adsorbates; N sites are not directly involved in catalytic reactions but they modify the electronic properties of Mo sites.

Photo-induced reactions in the ion-molecule complex Mg+-OCNC2H5

Ion - molecule complexes of magnesium cation with ethyl isocyanate were produced in a laser- ablation supersonic expansion nozzle source. Photo- induced reactions in the 1: 1 complexes have been studied in the spectral range of 230 - 410 nm. Photodissociation mass spectrometry revealed the persistent product Mg+ from nonreactive quenching throughout the entire wavelength range. As for the reactive channels, the photoproducts, Mg+OCN and C2H5+, were produced only in the blue absorption band of the complex with low yields. The action spectrum of Mg+(OCNC2H5) consists of two pronounced peaks on the red and blue sides of the Mg+ 3(2)P <-- 3(2)S atomic transition. The ground state geometry of Mg+ - OCNC2H5 was fully optimized at B3LYP/6- 31 - G** level by using GAUSSIAN 98 package. The calculated absorption spectrum of the complex using the optimized structure of its ground state agrees well with the observed action spectrum. Photofragment branching fractions of the products are almost independent of the photolysis photon energy for the 3P(x,y,z) excitations. The very low branching ratio of reactive products to nonreactive fragment suggests that evaporation is the main relaxation pathway in the photo- induced reactions of Mg+ (OCNC2H5). (C) 2003 American Institute of Physics.

Promoting effects in hydrogenation and hydrodesulfurization reactions on the zirconia and titania supported catalysts

Tetralin hydrogenation (HYD) and thiophene hydrodesulfurization (HDS) were studied for the supported MoS2 and WS2 sulfides, either non-promoted or promoted with Co and Ni. The supports used were ZrO2, alumina-stabilized TiO2 and pure alumina. Preparation of catalysts included presulfidation of non-promoted system with subsequent addition of promoter and resulfidation. It has been found that the nature of promoter plays determining role for the catalytic performance. The most active in both HYD and HDS reactions are Ni-promoted Mo and W catalysts, supported on ZrO2. (C) 2003 Published by Elsevier B.V.

Proton transfer reactions within the pyridazine-methanol cluster ion

The multiphoton ionization of the hydrogen-bonding cluster pyridazine-methanol (C4H4N2-CH3OH) was studied using a time-of-flight mass spectrometer at the wavelengths of 355 and 532 nm. At both wavelengths, a series of protonated C4H4N2-(CH3OH)(n)-H+ cluster ions were obtained. Relevant ab initio calculations were performed with HF and B3LYP methods. Equilibrium geometries of both neutral and ionic C4H4N2-CH3OH clusters, and dissociation channels and dissociation energies of ionic clusters, are presented. The results show that when C4H4N2-CH3OH is vertically ionized, C4H4N2H+ and CH3O are the dominant products via proton transfer reaction. A high energy barrier makes another channel corresponding to the production of C4H4N2H+ and CH2OH disfavored. (C) 2002 Elsevier Science B.V. All rights reserved.

Asymmetric cyclopropanation of styrene catalyzed by Cu-(chiral Schiff-base) complexes

Asymmetric cyclopropanation of olefins was carried out with chiral copper-Schiff base complexes derived from copper acetate monohydrate, substituted salicylaldehydes and a chiral amino alcohol. Substituents on salicylaldehyde framework demonstrate a significant effect on the steroselectivities. Those with electron-withdrawing properties enhance the selectivities, whereas bulky sustituents in ortho position to the phenol hydroxy group decrease the selectivities. An ee of more than 98% was achieved for the reaction of styrene with diazoacetate. (C) 2000 Elsevier Science Ltd. All rights reserved.